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EP2311078A1 - Patterned integrated circuit and method of production thereof - Google Patents

Patterned integrated circuit and method of production thereof

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Publication number
EP2311078A1
EP2311078A1 EP09771083A EP09771083A EP2311078A1 EP 2311078 A1 EP2311078 A1 EP 2311078A1 EP 09771083 A EP09771083 A EP 09771083A EP 09771083 A EP09771083 A EP 09771083A EP 2311078 A1 EP2311078 A1 EP 2311078A1
Authority
EP
European Patent Office
Prior art keywords
layer
list
ribtan
organic compound
electrical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09771083A
Other languages
German (de)
French (fr)
Other versions
EP2311078A4 (en
Inventor
Steven Grant Duvall
Pavel Khokhlov
Pavel I. Lazarev
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Carben Semicon Ltd
Original Assignee
Carben Semicon Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Carben Semicon Ltd filed Critical Carben Semicon Ltd
Publication of EP2311078A1 publication Critical patent/EP2311078A1/en
Publication of EP2311078A4 publication Critical patent/EP2311078A4/en
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/53204—Conductive materials
    • H01L23/53276—Conductive materials containing carbon, e.g. fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic Table
    • H01L29/1606—Graphene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/621—Providing a shape to conductive layers, e.g. patterning or selective deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings

Definitions

  • the present invention relates to patterned graphene-like carbon-based integrated circuits macro- and micro-electronics and methods for production thereof.
  • a silicon wafer is lithographically patterned to form a large number of interconnected electronic components (transistors, resistors, capacitors, etc) and arrays of thin film transistors for flat panel displays.
  • the technology is built upon the semiconducting properties of silicon and on lithographic patterning methods.
  • Increasing the density of electronic components and reducing the power consumption per component are two of the most important objectives in the microelectronics industry. These objectives have driven the steady advance in manufacturing technology and reduction in the size of the components over the past decades.
  • miniaturization of silicon-based electronics will reach an ultimate limit in the near future, primarily because of limitations imposed by the material properties of silicon and doped silicon, at the nanoscale.
  • Molecular electronics is considered to be an attractive alternative to the silicon- based electronics.
  • Molecular electronics utilizes molecular building blocks for the fabrication of electronic components.
  • Carbon nanotubes are considered to be particularly attractive candidates for the building blocks of molecular electronics.
  • Carbon nanotubes are essentially graphite tubes comprising several (one to over 100) graphene layers in tubular configurations.
  • a graphene layer consists of a single layer of sp 2 carbon atoms arranged in a hexagonal pattern with each atom (except those at the edges) chemically connected to its three neighbors.
  • Crystalline graphite consists of the stacked graphene layers.
  • Nanotubes conduct electrons in either a metallic mode or semiconducting mode depending on their specific structure. They have been found to be one-dimensional ballistic conductors over micron-scale distances at room temperature. The bandgap of semiconducting nanotubes depends on the diameter of the nanotube, hence it can be tuned by adjusting the diameter. Nanotubes can sustain very large currents (up to 1 mA), and sp 2 -sp 2 carbon bond ranks among the strongest in nature, making nanotubes exceptionally stable compared to other molecules.
  • nanotubes have been demonstrated to be capable of forming field-effect transistors and small integrated circuits, involving up to three carbon nanotubes.
  • These structures consist of several carbon nanotubes which are deposited on an insulating substrate and interconnected with metal wires that are lithographically patterned on top of the nanotubes.
  • the present invention provides patterned graphene-like carbon-based integrated circuits and methods of production thereof - which overcome the above mentioned drawbacks of conventional, silicon-based integrated circuits and alternative molecular electronics technologies.
  • the present invention provides a method of lithography patterning, comprising: a) formation of a ribtan layer, comprising the sequence of following steps:
  • CC is a predominantly planar carbon-conjugated core
  • A is a hetero-atomic group
  • p is O, 1, 2, 3, 4, 5, 6, 7, or 8
  • S 1 , S 2 , S3 and S 4 are substituents, ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8;
  • annealing with formation of a ribtan layer comprising graphene-like carbon- based structures, wherein said annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of the hetero-atomic groups and the substituents from the layer, and 2) fusion of the carbon- conjugated residues in order to form the predominantly planar graphene-like carbon-based structures; and b) formation of a pattern in the multilayer structure by one of lithographic methods, comprising the sequence of following steps: (iv) formation of a resist layer on the multilayer structure;
  • the present invention provides a method of thermal patterning, comprising the following steps:
  • CC is a predominantly planar carbon-conjugated core
  • A is a hetero-atomic group
  • p is 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • S 1 , S 2 , S3 and S 4 are substituent
  • ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8
  • the present invention provides a method of direct lithographic patterning, comprising the sequence of following steps: - depositing a wet pattern on a substrate using a solution which comprises at least one ⁇ - conjugated organic compound of the general structural formula I or a combination of the organic compounds of the general structural formula I:
  • CC is a predominantly planar carbon-conjugated core
  • A is a hetero-atomic group
  • p is 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • Si, S 2 , S3 and S 4 are substituent
  • ml, ml, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8;
  • annealing with the formation of a solid pattern comprising graphene-like carbon-based structures and possessing electrical-conductivity, wherein said annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of hetero-atomic groups and substituents from the solid pattern and 2) fusion of the carbon-conjugated residues in order to form the predominantly planar graphene-like carbon-based structures.
  • the present invention provides an integrated circuit, comprising a ribtan layer on the substrate, wherein the ribtan layer is patterned to define at least one functional structure, wherein the method of patterning is any of the methods of patterning disclosed in the present invention.
  • Figure 1 shows chemical formulas of six isomers of Bis (carboxybenzimidazoles) of Perylenetetracarboxylic acids
  • Figure 2 shows chemical formulas of mixture of 2-oxo-2,3-dihydro-l"H-l,2':r,2"- terbenzimidazoletricarboxylic acids and 2-oxo-2,3-dihydro-l'H-l,2'-bibenzimidazole- dicarboxylic acids;
  • Figure 3 schematically shows the disclosed ribtan layer after the drying step, wherein the planes of ⁇ -conjugated organic compound are oriented predominantly perpendicularly to the substrate surface;
  • Figure 4 shows the typical annealing regime disclosed
  • Figure 5 shows the results of thermo-gravimetric analysis of the bis-carboxy DBI
  • Figure 6 schematically shows the disclosed ribtan layer after the pyrolysis of the organic compound, wherein the planes of carbon-conjugated residues are oriented predominantly perpendicularly to the substrate surface;
  • Figure 7 schematically shows a graphene-like carbon-based structure;
  • Figure 8 schematically shows an embodiment of the disclosed ribtan layer, wherein the planes of graphene-like carbon-based structures are oriented predominantly perpendicularly to the substrate surface;
  • Figure 9 shows TEM image of bis-carboxy DBIPTCA annealed at 650 0 C for 30 minutes
  • Figure 10 shows electron diffraction on bis-carboxy DBIPTCA ribtan layer annealed at 650 0 C for 30 minutes;
  • Figure 11 shows absorption spectra of the annealed and dried layer of bis-carboxy DBI PTCA;
  • Figure 12 shows Raman spectra of the annealed samples;
  • Figure 13 shows Raman spectra at different points of the sample
  • Figures 14 shows resistivity as a function of maximum annealing temperature
  • Figure 15 shows resistivity as a function of time of a sample exposure at maximum temperature
  • Figure 16 shows the voltage-current characteristics obtained at different annealing temperatures on bis-carboxy DBIPTCA layer
  • Figure 17 schematically shows an embodiment of the disclosed ribtan layer, wherein the planes of graphene-like carbon-based structures are oriented predominantly parallel to the substrate surface;
  • Figures 18-22 schematically show a series of process steps of photolithographic patterning of ribtan layer according to the present invention
  • Figures 23-27 schematically show a series of process steps of electron-beam projection lithographic patterning of ribtan layer according to the present invention
  • Figure 28 shows a schematic diagram of EUV lithographic system used for an extreme-ultraviolet lithographic patterning of ribtan layer according to the present invention
  • Figures 29-33 schematically show a series of process steps of one embodiment of an imprint patterning of ribtan layer according to the present invention
  • Figures 34-38 schematically show a series of process steps of another embodiment of a thermal imprint patterning of ribtan layer according to the present invention
  • Figures 39-42 schematically show a series of process steps of another embodiment of a reverse imprint patterning of ribtan layer according to the present invention.
  • Figures 43-47 schematically show a series of process steps of another embodiment of an imprint patterning of ribtan layer according to the present invention.
  • FIGS 48-53 schematically show top views of an integrated circuit according to the present invention.
  • Figures 54-72 illustrate a method of formation of a multilayer structure with two ribtan layers patterned by disclosed methods.
  • Ribtan is a carbon material which can exist in two modification: 1) it can consist of aligned graphene- like nanoribbons which are aligned parallel to each other and perpendicular (edge-on) to surface of substrate, and 2) it can consist of aligned graphene-like sheets which are aligned parallel to each other and parallel (face-on or homeotropic) to the surface of substrate.
  • Graphene-like nanoribbons are narrow strips of graphene - one-atom-thick planar sheet of sp 2 -bonded carbon atoms that are densely packed in a honeycomb crystal lattice.
  • Graphene- like sheets are wide sheets of graphene - one-atom-thick planar sheet of sp 2 -bonded carbon atoms that are densely packed in a honeycomb crystal lattice.
  • the layers made of ribtan will be hereinafter named as ribtan layers.
  • Technology of ribtan layers production will be hereinafter named ribtan technology.
  • the ribtan technology is based on a thermally induced carbonization of organic compounds with predominantly planar carbon-conjugated cores.
  • Ribtan technology comprises a sequence of technological steps.
  • the first step in ribtan technology is cascade crystallization process.
  • Cascade crystallization is a method of the consecutive multi-step crystallization process for production of the solid precursor layers with ordered structure.
  • the process involves a chemical modification step and several steps of ordering during the formation of the solid precursor layer.
  • the chemical modification step introduces hydrophilic groups on the periphery of the molecule in order to impart amphiphilic properties to the molecule. Amphiphilic molecules stack together into supramolecules. The specific concentration is chosen, at which supramolecules are converted into a liquid-crystalline state to form a lyotropic liquid crystal (LLC), which is the next step of ordering.
  • LLC lyotropic liquid crystal
  • the LLC is deposited under the action of a shear force onto a substrate, so that the shear force direction determines the crystal axis direction in the resulting solid precursor layer.
  • This shear-force - assisted directional deposition is the next step of ordering, representing the global ordering of the crystalline or polycrystalline structure on the substrate surface.
  • the last step of the process is drying/crystallization, which converts the lyotropic liquid crystal into a solid precursor layer with highly ordered molecular structure.
  • Planes of ⁇ -conjugated molecules in the formed precursor layer can be aligned parallel (face-on or homeotropic) or perpendicular (edge-on) to the surface of substrate depending on molecular structure and /or coating technique.
  • Control over the precursor layer structure allows formation of layers comprising continuous graphene-like nanoribbons or graphene-like sheets with high electron mobility and low resistivity during carbonization process.
  • Cascade crystallization is followed by carbonization process named hereinafter as a step of formation of the metallic ribtan layer.
  • Carbonization is the term for a set of conversion reaction of an organic substance into carbon. Carbonization is usually a heating cycle. Carbonization might be performed with a heater such as a radiating heater, resistive heater, heater using an ac-electric or magnetic field, heater using a flow of heated liquid, and heater using a flow of heated gas.
  • Carbonization is performed in a reducing or inert atmosphere with a simultaneous slow heating, over a range of temperature that varies with the nature of the particular precursor and may extend to 2500 0 C. Carbonization is usually a complex process and several reactions may take place sequentially or simultaneously such as pyro lysis and fusion. Also carbonization process may be enhanced by addition of gas- phase or liquid-phase catalyst or reagents.
  • the first stage of carbonization is a pyrolysis process.
  • Pyrolysis is the chemical decomposition of a condensed substance. Common products of pyrolysis are volatile compounds containing non-carbon atoms and solid carbon residue. Preferably the diffusion of the volatile compounds to the atmosphere occurs slowly to avoid disruption and rupture of the carbon network. As a result, carbonization is usually a slow process. Its duration may vary considerably depending on the composition of the end-product, type of precursor, thickness of the material, and other factors. Pyrolysis process converts the solid precursor layer into essentially all carbon (product of pyrolysis).
  • the second stage of carbonization is a fusion reaction.
  • Fusion in other words condensation or polymerization
  • ribtan technology is chemical reactions between neighboring molecules or their pyrolized residues and which lead to growth of continuous graphene-like nanoribbons (in case of edge-on orientation of molecules in precursor layer) or stacked graphene-like sheets (in case of homeotropic precursor layer).
  • Several intermediate materials are formed during carbonization process.
  • Product of pyrolysis consists of carbon cores separated by gaps. All structural parameters of the pyrolysis product (interplanar spacing; structure of residual carbon cores; dimensions of gaps between residual carbon cores and their concentration; orientation of carbon cores in respect to the substrate surface) are determined by structure of a precursor layer.
  • Fusion process of product of pyrolysis leads to formation of an array of graphene-like nanoribbons or stacked graphene-like sheets with gaps.
  • atomic structure of the nanoribbons or sheets with gaps is similar to the product of pyrolysis, but islands of sp 2 carbon atoms grow and get ribbon-like or sheet-like morphology.
  • Structural parameters of the nanoribbons or sheets with gaps such as structure of residual carbon cores, dimensions of gaps between residual carbon cores and their concentration - are determined by parameters of carbonization process including but not limited to temperature, time, composition and pressure of ambient gas. Interplanar spacing and orientation of carbon cores in respect to the substrate surface depends on structure of precursor layer.
  • the intermediate materials described above have different electronic properties, especially conductivity.
  • Mobility of charge carriers within graphene-like nanoribbon or graphene-like sheet reaches high values, which are approximately equal to 2*10 5 Cm 2 V 1 S "1 .
  • Mobile charge carriers overcome the gaps between the graphene-like nanoribbons by hopping, and this conductivity is named hopping conductivity.
  • Electrical properties of the intermediate material depend on the concentration of gaps in the graphene-like nanoribbons or graphene-like sheets. Larger concentration of gaps leads to a smaller total electrical conductivity of the layer.
  • the layers can be formed in any of three states: insulating, semiconducting and metallic. The semiconducting state and the metallic state can be characterized as electrical-conducting states.
  • the material In the insulating state the material has resistivity in the range of 10 8 ⁇ *cm to 10 18 ⁇ *cm. In the semiconducting state, the resistivity of the material is in the range of lO ⁇ cm to 10 8 ⁇ *cm.
  • the resistivity of the material is in the range of 10 ⁇ 6 ⁇ *cm to lO ⁇ cm.
  • the width of these graphene-like nanoribbons is selected so as to control the energy gap in electron energy distribution spectrum that is formed due to quantum- dimensional effects. Formation of the ordered graphene-like nanoribbons by fusion reaction in the ribtan structure allows precise control of a nanoribbon width simply by controlling the layer thickness.
  • the precursor layer thickness depends only on solution concentration and coating parameters for layers obtained from LLC solution.
  • the ribtan technology allows the high volume production of ribtan layers over large surface (from several square millimeters to several square meters or larger). It allows low- cost manufacturing of the ribtan material for a broad range of different electronic devices, including integrated circuits.
  • the present invention provides a method of lithography patterning, comprising: a) formation of a ribtan layer, comprising the sequence of following steps: (i) application of a solution on a substrate, wherein the solution comprises at least one ⁇ -conjugated organic compound of a general structural formula I or any combination thereof:
  • CC is a predominantly planar carbon-conjugated core
  • A is a hetero-atomic group
  • p is 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • Si, S 2 , S3 and S 4 are substituents
  • ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8
  • drying and (iii) annealing with formation of a layer comprising graphene-like carbon-based structures, wherein said annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of the hetero-atomic groups and the substituents from the layer, and 2) fusion of the carbon-conjugated residues in order to form the predominantly planar graphene-like carbon- based structures; and b) formation of a pattern
  • the step of the electrical-conducting ribtan layer formation further comprises a formation of at least one additional layer.
  • the formation of at least one additional layer is carried out after the annealing step.
  • the additional layers comprise dielectric materials, semiconductor material, metals or any combination thereof.
  • the dielectric material is formed from an insulating material and selected from the list comprising insulating ribtan material, silicon dioxide (SiO 2 ), silicon nitride (Si 3 N 4 ), aluminum oxide (AI2O3), hafnium oxide
  • the conductor is selected from the list comprising copper, gold, silver, zinc, tin, indium, aluminum, titanium, doped poly- silicon, conductive ribtan layer as a semi-metal conductor, and any combination thereof.
  • the substrate is made of one or several materials of the list comprising Si, Ge, SiGe, GaAs, diamond, quartz, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, metals, and any combination thereof.
  • the substrate further comprises doped regions, circuit features, multilevel interconnects, and at least one patterned electrical-conducting ribtan layer.
  • the electrical-conducting ribtan layer possesses anisotropy of conductivity. In another embodiment, the electrical-conducting ribtan layer possesses an optical anisotropy. In still another embodiment, the graphene-like carbon-based structures are globally ordered on the substrate surface.
  • the disclosed electrical-conducting ribtan layer has a global order or, in other words, such layer has globally ordered graphene-like carbon-based structures.
  • Disclosed layer possesses the long- range order which is characterized by spatial correlation of graphene-like carbon-based structures within the limits of an entire layer. Spacing between the structures is approximately equal to 3.4 ⁇ 0.1 A in the direction approximately parallel to one of crystallographic axis over the entire substrate surface.
  • Such spatial periodicity means that the electrical-conducting ribtan layer possesses the long-range coordination order.
  • the disclosed layer may possess the long-range orientation order when hexagonal cells of graphene-like carbon-based structures are orientated substantially uniformly.
  • the manufacturing process controls the direction of the crystallographic axes of the electrical- conducting layer over the entire substrate surface.
  • the structure of the electrical- conducting layer differs from the structure of a polycrystalline layer, in which the uniform crystalline structure is formed within a separate crystal grain.
  • the square of such a grain is much smaller than that of the substrate surface.
  • the substrate surface has a limited influence on the crystal structure of the electrical-conducting layer, and consequently on the properties of electrical-conducting layer.
  • the electrical-conducting layer may be formed on a part of the substrate surface, depending on the system design requirements.
  • the electrical-conducting ribtan layer possesses semiconductor conductivity of n-type.
  • the electrical-conducting ribtan layer possesses semiconductor conductivity of p-type.
  • the electrical-conducting ribtan layer possesses electrical conductivity approximating to metal-type conductivity.
  • the graphene-like carbon-based structures have the form selected from the list comprising disk, plate, lamella, ribbon or any combination thereof.
  • the distance between planes of the graphene-like carbon-based structures approximately equals to 3.4 ⁇ 0.1 A.
  • said organic compound comprises at least one rylene fragment.
  • Table 1 shows some examples of heterocyclic molecular systems comprising one or more rylene fragments of a general structural formula corresponding to structures 1-23.
  • said organic compound comprises one or more anthrone fragment.
  • Table 2 shows some examples of organic compounds comprising the anthrone fragments of a general structural formula corresponding to structures 24 - 31. Table 2. Examples of planar polycyclic molecular systems comprising anthrone fragments
  • the organic compound comprises planar fused polycyclic hydrocarbon.
  • Table 3 shows some examples of the planar fused polycyclic hydrocarbons selected from the list comprising truxene, decacyclene, antanthrene, hexabenzotriphenylene, 1.2,3.4,5.6,7.8-tetra-(peri-naphthylene)- anthracene, dibenzoctacene, tetrabenzoheptacene, peropyrene, hexabenzocoronene, violanthrene, isoviolanthrene and of a general structural formula corresponding to structures 32-43.
  • the organic compound comprises one or more coronene fragment.
  • Table 4 shows some examples of organic compounds comprising the coronene fragments of a general structural formula corresponding to structures 44-51.
  • At least one of the hetero-atomic groups A is selected from the list comprising imidazole group, benzimidazole group, amide group, substituted amide group, and hetero-atom selected from nitrogen, oxygen, and sulfur.
  • At least one of the substituents S 1 , S 2 , S 3 and S 4 provides solubility of the organic compound in water or aqueous solution and is independently selected from the list comprising COO , SO3 , HPO3 , and PO3 2 and any combination thereof.
  • at least one of the substituents S 1 , S 2 , S 3 and S 4 provides solubility of the organic compound in water or aqueous solution and is independently selected from the list comprising COO , SO3 , HPO3 , and PO3 2 and any combination thereof.
  • S 1 , S 2 , S 3 and S 4 provides solubility of the organic compound in organic solvents and is independently selected from the list comprising CONR 1 R 2 , CONHCONH 2 , SO 2 NR 1 R 2 , R 3 , or any combination thereof, wherein R 1 , R 2 and R 3 are selected from hydrogen, an alkyl group, an aryl group, and any combination thereof, where the alkyl group has the general formula -(CH 2 ) n CH 3 , where n is an integer from O to 27, and the aryl group is selected from the list comprising phenyl, benzyl and naphthyl.
  • At least one of the substituents Si, S 2 , S 3 and S 4 provides solubility of the organic compound in organic solvents and is selected from the list comprising (Ci-C 3 s)alkyl, (C 2 -C 3 s)alkenyl, and (C 2 -C 35 )alkinyl.
  • At least one of the substituents S 1 , S 2 , S3 and S 4 provides solubility of the organic compound in organic solvents and comprises fragments selected from the list comprising structures 52-58 shown in Table 5, where R is selected from a list comprising linear or branched (Ci-C 35 ) alkyl, (C 2 -C 35 )alkenyl, and (C 2 -C 35 )alkinyl.
  • the organic compound is capable of forming rod-like supramolecules in the solution via ⁇ - ⁇ - interaction between the adjacent carbon-conjugated cores.
  • the disclosed method further comprises a step of the application of an external alignment action upon the applied solution in order to provide aligned orientation of the rod-like supramolecules.
  • the application and alignment steps are carried out simultaneously.
  • the alignment step is carried out after the application step.
  • the rod- like supramolecules are aligned in the substrate plane.
  • At least one of the substituents Si, S 2 , S 3 and S 4 comprises molecular binding groups which number and arrangement provide for the formation of planar supramolecules from the organic compound molecules in the solution via non-covalent chemical bonds.
  • at least one binding group is selected from the list comprising a hydrogen acceptor (A H ), a hydrogen donor (D R ), and a group having the general structural formula II
  • the hydrogen acceptor (A H ) and hydrogen donor (D H ) are independently selected from the list comprising NH-group, and oxygen (O).
  • at least one of the binding groups is selected from the list comprising hetero-atoms, COOH, SO 3 H, H 2 PO 3 , NH, NH 2 , CO, OH, NHR, NR, COOMe, CONH 2 , CONHNH 2 , SO 2 NH 2 , -SO 2 -NH-SO 2 -NH 2 and any combination thereof, where radical R is an alkyl group or an aryl group, the alkyl group having the general formula -(CH 2 ) n CH 3 , where n is an integer from O to 27, and the aryl group being selected from the list comprising phenyl, benzyl and naphthyl.
  • At least one of the substituents S 1 , S 2 , S 3 and S 4 is selected from the list comprising -NO 2 , -Cl, -Br, -F, -CF 3 , -CN, -OCH 3 , -OC 2 H 5 , -OCOCH 3 , -OCN, -SCN, and -NHCOCH 3 .
  • the non-covalent chemical bonds are independently selected from the list comprising a single hydrogen bond, dipole-dipole interaction, cation - pi-interaction, Van-der-Waals interaction, coordination bond, ionic bond, ion-dipole interaction, multiple hydrogen bond, interaction via the hetero-atoms and any combination thereof.
  • the planar supramolecule have the form selected from the list comprising disk, plate, lamella, ribbon or any combination thereof.
  • the planar supramolecules are predominantly oriented in the plane of the substrate.
  • the drying and annealing steps are carried out simultaneously. In another embodiment, the drying and annealing steps are carried out sequentially.
  • the lithographic method is a photolithographic method, wherein the resist layer is a photoresist layer.
  • the formation of the photoresist layer comprises the following steps: treatment of the electrical-conducting ribtan layer in order to clean said electrical-conducting ribtan layer and increase adhesion of the photoresist layer to the electrical-conducting ribtan layer; coating of the photoresist layer by one or several methods selected from the list comprising spin coating, spray coating, flooding, and electrostatic method; and soft baking.
  • the photoresist is a positive photoresist.
  • the photoresist is a negative photoresist.
  • the formation of the pattern in the photoresist layer comprises the following steps: alignment of a mask with the electrical- conducting ribtan layer; exposure of the photoresist layer by means of light radiation through the mask; development of the photoresist layer; rinsing and drying of the electrical- conducting ribtan layer; and post-baking of the patterned photoresist layer.
  • the formation of the pattern in the photoresist layer further comprises a soft baking step after the step exposure of the photoresist layer by means of light radiation through the mask.
  • the exposure step is carried out by means of ultraviolet radiation, wherein a spectral range is defined by the photoresist used.
  • the exposure step is carried out by means of a contact printing which is applied to the entire wafer, wherein the electrical-conducting ribtan layer is brought into the surface contact with the mask.
  • the exposure step is carried out by means of proximity printing which is applied to the entire electrical-conducting ribtan layer, wherein there is a gap between the electrical-conducting ribtan layer and the mask.
  • the exposure step is carried out by means of projection printing which is applied only to portions of the electrical-conducting ribtan layer, wherein there is a gap between the electrical-conducting ribtan layer and the mask.
  • the transfer step further comprises the following steps: etching of the electrical-conducting ribtan layer, wherein the layer is located underneath the patterned photoresist layer; and removing of the patterned photoresist layer.
  • the etching is by a wet etching method.
  • the etching is a dry-etching method selected from a list comprising plasma etching, reactive ion etching (RIE), sputter etching, magnetically enhanced RIE (MERIE), reactive ion beam etching, high-density plasma etching.
  • the mask is a phase-shifting mask.
  • the patterning lithographic method is an electron-beam projection lithographic method, wherein the resist layer is an electron resist layer.
  • the formation of the electron resist layer comprises the following steps: treatment of the electrical-conducting ribtan layer in order to clean the electrical-conducting ribtan layer and increase adhesion of the electron resist layer to the electrical-conducting ribtan layer; coating of the electron resist layer by one or several methods selected from the list comprising spin coating, spray coating, flooding, and electrostatic method, and drying of the electron resist layer.
  • the electron resist is a positive electron resist.
  • the electron resist is a negative electron resist.
  • the polymer-electron interaction causes chemical bonds to be broken to form shorter molecular fragments.
  • the molecular weight is reduced in the irradiated area, which can be dissolved subsequently in a developer solution that attacks the low-molecular-weight material.
  • the irradiation causes a radiation-induced polymer linking.
  • the cross linking creates a complex three-dimensional structure with a molecular weight higher than that of the non-irradiated polymer.
  • the non-irradiated electron resist can be dissolved in a developer solution that does not attack the high-molecular-weight material.
  • the formation of the pattern in the electron resist layer comprises the following steps: alignment of the mask with the electrical-conducting ribtan layer; exposure of the electron resist layer by means of electron- beam radiation through the mask; development of the electron resist layer; rinsing and drying of the electrical-conducting ribtan layer; and post-baking of the patterned electron resist layer.
  • the transfer step further comprises the following steps: etching of the electrical-conducting ribtan layer, wherein the layer is located underneath the patterned electron resist layer; and removing of the patterned electron resist layer.
  • the etching is a wet etching method.
  • the etching is a dry-etch method selected from a list comprising plasma etching, reactive ion etching (RIE), sputter etching, magnetically enhanced RIE (MERIE), reactive ion beam etching, and high-density plasma etching.
  • the mask is an electron scattering mask.
  • the patterning lithographic method is an extreme-ultraviolet lithographic method, wherein the resist layer is a photoresist layer.
  • the spectral range of extreme-ultraviolet radiation is determined by the photoresist used.
  • the formation of the patterned photoresist layer further comprises a reflection mask.
  • the spectral range is approximately from 10 to 14 nanometers.
  • the lithographic method is an imprint photolithographic method
  • the resist layer is an imprint resist layer.
  • the formation of the imprint layer comprises following steps:
  • - coating of the imprint resist layer by one or several methods selected from the list comprising spin coating, spray coating, flooding, and electrostatic method; and - drying of the imprint resist layer.
  • the imprint resist is a thermal plastic material.
  • the formation of the pattern in the imprint resist layer comprises following steps:
  • the hard mould may be made of materials selected from the list comprising silicon, silicon dioxide, silicon carbide, silicon nitride, sapphire, and diamond.
  • the features have nano-scale sizes.
  • the present invention provides a method of thermal patterning, comprising the following steps: application of a solution on a substrate, wherein the solution comprising at least one ⁇ -conjugated organic compound of a general structural formula I or any combination thereof:
  • CC is a predominantly planar carbon-conjugated core
  • A is a hetero-atomic group
  • p is 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • S 1 , S 2 , S3 and S 4 are substituents
  • ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8; drying with formation of a solid layer, and formation of a pattern in the solid layer by a local annealing, wherein the local annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of the hetero-atomic groups and the substituents from the solid layer and 2) fusion of the carbon-conjugated residues in order to form the predominantly planar graphene-like carbon-based structures.
  • the substrate is made of one or several materials of the list comprising Si, Ge, SiGe, GaAs, diamond, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, and metals, and any combination thereof.
  • the substrate may further comprise doped regions, circuit features, multilevel interconnects, and at least one patterned ribtan layer.
  • the substrate is a heat-sensitive substrate.
  • the organic compound comprises one or more rylene fragments.
  • Examples of the organic compounds 1 - 23 are given in Table 1.
  • the organic compound comprises one or more anthrone fragments.
  • Examples of the organic compounds 24 - 31 are given in Table 2.
  • the organic compound comprises planar fused polycyclic hydrocarbon.
  • hydrocarbons comprising truxene, decacyclene, antanthrene, hexabenzotriphenylene, 1.2,3.4,5.6,7.8-tetra-(peri- naphthylene)-anthracene, dibenzoctacene, tetrabenzoheptacene, peropyrene, hexabenzocoronene, violanthrene, isoviolanthrene (structures 32 - 43) are given in Table 3.
  • the organic compound comprises one or more coronene fragments.
  • Examples of the organic compounds 44 - 51 are given in Table 4.
  • at least one of the hetero-atomic groups A is selected from the list comprising imidazole group, benzimidazole group, amide group, substituted amide group, and hetero-atom selected from nitrogen, oxygen, and sulfur.
  • At least one of the substituents S 1 , S 2 , S 3 and S 4 provides solubility of the organic compound in water or aqueous solution and is selected from the list comprising COO , SO3 , HPO3 , and PO3 2 , and any combination thereof.
  • At least one of the substituents S 1 , S 2 , S3 and S 4 provides solubility of the organic compound in organic solvents and is selected from the list comprising CONR 1 R 2 , CONHCONH 2 , SO 2 NR 1 R 2 , R 3 , or any combination thereof, wherein R 1 , R 2 and R 3 are selected from hydrogen, an alkyl group, an aryl group, and any combination thereof, where the alkyl group has the general formula -(CH 2 ) n CH 3 , where n is an integer from O to 27, and the aryl group is selected from the list comprising phenyl, benzyl and naphthyl.
  • At least one of the substituents S 1 , S 2 , S 3 and S 4 provides solubility of the organic compound in organic solvents and is selected from the list comprising (Ci-C 3 s)alkyl, (C 2 -C 3 s)alkenyl, and (C 2 - C35)alkinyl.
  • At least one of the substituents S 1 , S 2 , S3 and S 4 provides solubility of the organic compound in organic solvents and comprises fragments selected from the list comprising structures 52-58 shown in Table 5, where R is selected from a list comprising linear or branched (C 1 -C 35 ) alkyl, (C 2 -C 35 )alkenyl, and (C 2 -C 35 )alkinyl.
  • the organic compound is capable of forming rod-like supramolecules in the solution via ⁇ - ⁇ - interaction between the adjacent carbon-conjugated cores.
  • the disclosed method further comprises a step of the application of an external alignment action upon the applied solution in order to provide aligned orientation of the rod-like supramolecules.
  • the application and alignment steps are carried out simultaneously.
  • the alignment step is carried out after the application step.
  • the rod-like supramolecules are aligned in the substrate plane.
  • At least one of said substituents S 1 , S 2 , S 3 and S 4 comprises at least one molecular binding group which number and arrangement provide for the formation of planar supramolecules from the organic compound molecules in the solution via non-covalent chemical bonds.
  • at least one binding group is selected from the list comprising a hydrogen acceptor (A H ), a hydrogen donor (D R ), and a group having a general structural formula II
  • the hydrogen acceptor (A R ) and hydrogen donor (D R ) are independently selected from the list comprising NH-group, and oxygen (O).
  • at least one of the binding groups is selected from the list comprising hetero-atoms, COOH, SO 3 H, H 2 PO 3 , NH, NH 2 , CO, OH, NHR, NR, COOMe, CONH 2 , CONHNH 2 , SO 2 NH 2 , -SO 2 -NH-SO 2 -NH 2 and any combination thereof, where radical R is an alkyl group or an aryl group, the alkyl group having the general formula -(CH 2 ) n CH 3 , where n is an integer from O to 27, and the aryl group being selected from the list comprising phenyl, benzyl and naphthyl.
  • At least one of substituents S 1 , S 2 , S 3 and S 4 is selected from the list comprising -NO 2 , -Cl, -Br, -F, -CF 3 , -CN, -OCH 3 , -OC 2 H 5 , -OCOCH 3 , -OCN, -SCN, and -NHCOCH 3 .
  • the non-covalent chemical bonds are independently selected from the list comprising a single hydrogen bond, dipole-dipole interaction, cation - pi-interaction, Van-der-Waals interaction, coordination bond, ionic bond, ion-dipole interaction, multiple hydrogen bond, interaction via the hetero-atoms, and any combination thereof.
  • the planar supramolecule have the form selected from the list comprising disk, plate, lamella, ribbon and any combination thereof.
  • the planar supramolecules are predominantly oriented in the plane of the substrate.
  • the local annealing is carried out by the laser thermal patterning process using one or several lasers.
  • the local annealing is carried out by a radiation selected from the list comprising electromagnetic radiation, X-ray, UV-radiation, infrared radiation, and any combination thereof.
  • the local annealing is carried out with a direct write technique.
  • the local annealing is carried out using a pattern transfer mask-based technique.
  • the local annealing is carried out by a heating element located in close proximity with the surface of the solid layer.
  • the heating element is a hard mould that contains features defined on its surface.
  • the features have nano-scale sizes.
  • the local annealing comprises the following sequence of steps:
  • the local annealing comprises the sequence of following steps:
  • the local annealing is carried out using a focused ultrasound beam and direct write technique.
  • the local annealing comprises the following sequence of steps:
  • the pattern to be transferred onto a multilayer structure may be formed on the surface of the multilayer structure using a positive resist.
  • An exothermic chemical reaction is created on the exposed areas of the pattern by introducing the chemicals known to one skilled in the art. This reaction creates local heating, which causes local annealing of the ribtan material.
  • the local annealing is carried out by applying local pressure to the surface of the solid layer.
  • the pattern to be transferred onto a multilayer structure is formed on one surface of a block of material forming a hard mould that contains features defined on its surface. The hard mould is applied to the surface of the multilayer structure with sufficient force to create local heating and deformation of the crystal structure, transferring the pattern into the ribtan layer.
  • the features may have nano-scale sizes.
  • the local annealing is carried out by passing a current through at least one portion of the solid layer.
  • the passing of the current is carried out using the scanning tunneling microscope (STM) tip, array of STM tips, electron beam, array of electron beams, and any combination thereof.
  • the local annealing is carried out by a DC, AC or pulsed electric current flowing between a hard mould, which comprises features defined on its surface and is brought into contact with the surface of the multilayer structure or into close proximity with the surface, and an electrode located on opposite surface of the multilayer structure.
  • the features have nano-scale sizes. Electricity is passed through the hard mould and the multilayer structure to the electrode, creating local heating and annealing the ribtan material.
  • the present invention provides a method of direct lithographic patterning, comprising the sequence of following steps: depositing a wet pattern on a substrate using a solution which comprises at least one ⁇ -conjugated organic compound of the general structural formula I or any combination thereof:
  • CC is a predominantly planar carbon-conjugated core
  • A is a hetero-atomic group
  • p is 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • S 1 , S 2 , S3 and S 4 are substituents
  • ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8
  • sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8
  • drying of the wet pattern with the formation of a solid pattern and annealing with the formation of a solid pattern comprising graphene-like carbon-based structures and possessing electrical- conductivity, wherein said annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of hetero-atomic groups and substituents from the solid pattern and 2) fusion of the carbon-conjugated residues in order to form the predominantly planar graphene
  • the method of direct lithographic patterning refers to methods in which patterns of materials are supplied to (and sometimes removed from) a substrate simply by physical contact or exposure through the mediating use of stamps, nozzles (e.g., inkjet printheads), or masks (e.g., silk screens).
  • the depositing step may be carried out by at least one of the techniques selected from the list comprising a printing, a reverse-imprinting, an ink-jet printing, a drawing by a ruling pen (drawing-pen), a dip-pen lithographic technique, and any combination thereof.
  • Direct printing methods can be used in an integrated circuit, from the metal contacts to the insulating elements to the active transport layers.
  • Direct printing methods may be either parallel or serial in their operation, depending upon how the pattern is defined.
  • Pattern definition may come, for example, from relief features on a stamp, from masks that protect regions on a substrate from exposure to a printed material, or by focused jets that trace a path across the substrate.
  • stamps The method of direct lithographic patterning which uses stamps may be successfully applied to many different areas of organic electronics. Their ability to pattern large areas in a single process step (i.e., their parallel operation) and their high resolution represent key features of these approaches.
  • a stamp supplies a solution which comprises at least one ⁇ -conjugated organic compound of the general structural formula I to a substrate by physical contact. This transferred material acts as a functional layer of an organic device or an integrated circuit.
  • the "stamps" used for this process come in widely different forms and can be made of materials ranging from rigid solids such as glass or silicon to flexible plastic sheets to soft, viscoelastic elastomers, most notably polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • stamps For large-area application, these stamps should be thin to enable bending that can facilitate their removal from rigid, nonflexible device substrates, such as thick glass or semiconductor wafers. Resolution limits are often very good, limited by the resolution of the stamps themselves or the materials characteristics of the solutions.
  • method of direct lithographic patterning reduces the number of process steps by minimizing the use of sacrificial layers or even eliminating them by employing purely additive approaches.
  • many of the methods are noninvasive, thermally and chemically, leading to simplicity in process engineering.
  • the depositing step further comprises preliminary microcontact printing of chemicals which may serve as templates for patterning solution comprising at least one ⁇ -conjugated organic compound of the general structural formula I by serving as wetting or de-wetting patterns.
  • ⁇ -conjugated organic compound of the general structural formula I by serving as wetting or de-wetting patterns.
  • a wide variety of printable materials can be employed for these approaches.
  • hydrophobic siloxane oligomers present in common PDMS elastomer transfer onto the contacted substrates. Those oligomer films can function as dewetting templates for patterning solution comprising at least one ⁇ -conjugated organic compound of the general structural formula I with resolution as good as 1 ⁇ m. The solution moistens the unstamped, hydrophilic surfaces but leaves the printed, hydrophobic surfaces dry.
  • microcontact printed templates may also be used as wetting patterns in which solutions comprising at least one ⁇ -conjugated organic compound of the general structural formula I are deposited on the printed regions and not on the bare regions, in contrast to the aforementioned embodiment.
  • the materials printed from a stamp are the actual functional materials for organic electronics, integrated circuits or other applications.
  • the advantages of this approach include, in many cases, the ability to pattern several types of solution comprising at least one ⁇ -conjugated organic compound of the general structural formula I on a single device substrate without exposing it to solvents or other invasive processing and high levels of resolution.
  • the requirements for these methods are: a stamp that can support the solutions and may be contacted to a substrate, and a mechanism for the transfer of this solution from the stamp to the substrate.
  • These substrates can use special surface chemistries, conformable adhesive layers, or other means to guide preferential adhesion.
  • the adhesive layer may be made of polyvinylbutyral or polyacrylate.
  • Stamps suitable for transfer printing may comprise soft elastomers, such as PDMS, and also hard backings, especially when pressure is applied to guide the transfer and/or when the substrate has a soft, conformable surface to facilitate contact.
  • the features of relief on the stamps usually define the patterns in the transfer printed materials. Solutions comprising at least one ⁇ - conjugated organic compound of the general structural formula I that are transfer-printed can form a variety of layers of organic electronic systems or integrated circuits, from conductors to semiconductors to dielectrics.
  • two parts of an organic device or integrated circuit may be fabricated separately whereupon these parts incorporate with each other.
  • the disclosed method is the stamp-based printing method for which two parts are joined for the fabrication and patterning of the materials.
  • Each part of the device can be formed by the disclosed method of direct lithographic patterning.
  • the disclosed method is similar to the well-known lamination technology - however in case of lamination the devices are formed by the incorporation of two parts but no material is transferred.
  • the substrate is made of one or several materials of the list comprising Si, Ge, SiGe, GaAs, diamond, quartz, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, metals and any combination thereof.
  • the substrate further comprises doped regions, circuit features, multilevel interconnects, and at least one patterned ribtan layer.
  • the organic compound comprises one or more rylene fragments.
  • Examples of the organic compounds 1 - 23 are given in Table 1.
  • the organic compound comprises one or more anthrone fragments.
  • Examples of the organic compounds 24 - 31 are given in Table 2.
  • the organic compound comprises planar fused poly cyclic hydrocarbons.
  • hydrocarbons comprising truxene, decacyclene, antanthrene, hexabenzotriphenylene, 1.2,3.4,5.6,7.8-tetra-(peri- naphthylene)-anthracene, dibenzoctacene, tetrabenzoheptacene, peropyrene, hexabenzocoronene, violanthrene, isoviolanthrene (structures 32 - 43) are given in Table 3.
  • the organic compound comprises one or more coronene fragments.
  • Examples of the organic compounds 44 - 51 are given in Table 4.
  • at least one of the hetero-atomic groups are given in Table 4.
  • A is selected from the list comprising imidazole group, benzimidazole group, amide group, substituted amide group, and hetero-atom selected from nitrogen, oxygen, and sulfur.
  • at least one of the substituents S 1 , S 2 , S3 and S 4 provides solubility of the organic compound in water or aqueous solution and is selected from the list comprising COO , SO3 , HPO3 , and PO3 2 and any combination thereof.
  • At least one of the substituents S 1 , S 2 , S3 and S 4 provides solubility of the organic compound in organic solvents and is selected from the list comprising CONR 1 R 2 , CONHCONH 2 , SO 2 NR 1 R 2 , R 3 , or any combination thereof, wherein R 1 , R 2 and R 3 are selected from hydrogen, an alkyl group, an aryl group, and any combination thereof, where the alkyl group has the general formula - (CH 2 ) n CH 3 , where n is an integer from O to 27, and the aryl group is selected from the list comprising phenyl, benzyl and naphthyl.
  • At least one of the substituents S 1 , S 2 , S3 and S 4 provides solubility of the organic compound in organic solvents and is selected from the list comprising (Ci-C 35 )alkyl, (C 2 - C 35 )alkenyl, and (C 2 -C 35 )alkinyl.
  • At least one of the substituents S 1 , S 2 , S3 and S 4 provides solubility of the organic compound in organic solvents and comprises fragments selected from the list comprising structures 52-58 shown in Table 5, where R is selected from a group comprising linear or branched (C 1 -C 35 ) alkyl, (C 2 -C 35 )alkenyl, and (C 2 -C 35 )alkinyl.
  • the organic compound is capable of forming rod-like supramolecules in the solution via ⁇ - ⁇ - interaction between the adjacent carbon-conjugated cores.
  • the disclosed method further comprises a step of the application of an external alignment action upon the applied solution in order to provide an aligned orientation of the rod-like supramolecules.
  • the application and alignment steps are carried out simultaneously.
  • the alignment step is carried out after the application step.
  • the rod-like supramolecules are aligned in the substrate plane.
  • the at least one of the substituents S 1 , S 2 , S 3 and S 4 comprises molecular binding groups which number and arrangement provide for the formation of planar supramolecules from the organic compound molecules in the solution via non-covalent chemical bonds.
  • at least one binding group is selected from the list comprising a hydrogen acceptor (A R ), a hydrogen donor (D R ), and a group having a general structural formula II
  • the hydrogen acceptor (A R ) and hydrogen donor (D R ) are independently selected from the list comprising NH-group, and oxygen (O).
  • at least one of the binding groups is selected from the list comprising hetero-atoms, COOH, SO3H, H 2 PO 3 , NH, NH 2 , CO, OH, NHR, NR, COOMe, CONH 2 , CONHNH 2 , SO 2 NH 2 , -SO 2 -NH- SO 2 -NH 2 and any combination thereof, where radical R is an alkyl group or an aryl group, the alkyl group having the general formula -(CH 2 ) n CH 3 , where n is an integer from O to 27, and the aryl group being selected from the list comprising phenyl, benzyl and naphthyl.
  • At least one of the substituents S 1 , S 2 , S 3 and S 4 is selected from the list comprising -NO 2 , -Cl, -Br, -F, -CF 3 , -CN, -OCH 3 , -OC 2 H 5 , -OCOCH 3 , -OCN, -SCN, and -NHCOCH 3 .
  • the non-covalent chemical bonds are independently selected from the list comprising a single hydrogen bond, dipole-dipole interaction, cation - pi-interaction, Van-der-Waals interaction, coordination bond, ionic bond, ion-dipole interaction, multiple hydrogen bond, interaction via the hetero-atoms and any combination thereof.
  • the planar supramolecules have the form selected from the list comprising disk, plate, lamella, ribbon or any combination thereof.
  • the planar supramolecules are predominantly oriented in the plane of the substrate.
  • the solution is an isotropic solution. In another embodiment of the disclosed method, said solution is a lyotropic liquid crystal solution. In still another embodiment, the disclosed method further comprises an alignment action, wherein the alignment action is simultaneous with application of the wet pattern on the substrate. In yet another embodiment of the disclosed method, the deposition step is carried out by at least one of techniques selected from the list comprising a printing, a reverse-imprinting, an ink-jet printing, a drawing by a ruling pen (drawing-pen), a dip-pen lithographic technique, and any combination thereof. In one embodiment of the disclosed method, the drying and annealing steps are carried out simultaneously. In another embodiment of the disclosed method, the drying and annealing steps are carried out sequentially.
  • One embodiment of the disclosed method is named thermal-imprint lithography, and for this method the step of deposition of a wet pattern on a substrate comprises
  • the solution comprises at least one ⁇ -conjugated organic compound of the general structural formula I and formation of a wet layer on the substrate;
  • the features have nano-scale sizes.
  • the drying of the wet layer is carried out during pressing the hard mould into the wet layer, and a solid layer with the thickness contrast is formed.
  • the disclosed method further comprises a step of transferring thickness contrast through the solid layer via an anisotropic etching process, wherein this step is carried out after the drying step.
  • the present invention provides an integrated circuit, comprising a ribtan layer on the substrate, wherein the ribtan layer is patterned to define at least one functional structure, wherein the method of patterning is any of the methods of patterning disclosed in the present invention.
  • the substrate is made of one or several materials of the list comprising Si, Ge, SiGe, GaAs, diamond, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, metals and any combination thereof.
  • the substrate further comprises doped regions, circuit features, multilevel interconnects, and at least one patterned ribtan layer.
  • the substrate comprises an insulator.
  • the ribtan layer has a graphene- like structure of nano-scale thickness.
  • the ribtan comprises at least one graphene-like strip.
  • the ribtan layer comprises at least one graphene-like carbon-based strip.
  • the ribtan layer is patterned to form at least one electronic device.
  • the electronic device comprises a transistor.
  • the transistor comprises a source electrode; a drain electrode, spaced apart from the source electrode; a connector being in electrical communication with both the source electrode and the drain electrode; and a gate electrode spaced apart from the connector at a distance such that an electron transport property of the connector changes when bias voltage is applied to the gate electrode so as to induce a field that interacts with the connector, and wherein the connector is made by patterning of ribtan layer.
  • at least one electrode selected from the list comprising a source electrode, a drain electrode and a gate electrode comprises the ribtan layer.
  • the electronic device comprises at least one logic gate. In another embodiment of the disclosed integrated circuit, the electronic device comprises at least one logic directional coupler.
  • the electronic device comprises at least one interferometer.
  • the interferometer comprises a source electrode; a drain electrode; a loop-like structure, having a first branch and a spaced-apart second branch being in electrical communication with the source electrode and with the drain electrode; at least one gate electrode disposed adjacent to the first branch, that is capable of exerting an electrical field substantially only on the first branch; and a sensor that may sense interference between electrons passing through the first branch and electrons passing through the second branch, and wherein the loop-like structure is made by patterning of ribtan layer.
  • at least one electrode selected from the list comprising a source electrode, a drain electrode and a gate electrode comprises the ribtan layer.
  • the interferometer comprises a Mach-Zender device.
  • Example 1 describes a formation of one embodiment of the electrical-conducting ribtan layer.
  • the ribtan layer comprising graphene-like carbon-based structures was formed by a mixture of bis(carboxybenzimidazoles) of prerylenetetracarboxylic acids (bis-carboxy DBI PTCA), which predominantly planar carbon-conjugated cores are shown in Table 1, ## 4 and 5.
  • bis-carboxy DBI PTCA prerylenetetracarboxylic acids
  • Table 1 a water solution of bis-carboxy DBI PTCA was applied on a substrate.
  • the solution comprised a mixture of six isomers as shown in Figure 1.
  • Bis- carboxy DBI PTCA is a ⁇ -conjugated organic compound, where the predominantly planar carbon-conjugated core (CC as in formula I) comprises rylene fragments, the benzimidazole groups serve as hetero-atomic groups and carboxylic groups serve as substituents providing solubility.
  • the molecular structure provides for the formation of rod-like supramolecules. Quartz was used as a substrate material as an example only. The Mayer rod technique was used to coat the water-based solution of bis -carboxy DBI PTCA. During the second step the drying was performed at 40 degrees C and humidity of approximately 70%. By the end of the drying step, the layer usually retained about 10% of the solvent.
  • the ribtan layer comprises rod-like supramolecules oriented along the coating direction.
  • Figure 3 schematically shows the supramolecule 1 oriented along the y-axis and located on the substrate 2.
  • the distance between planes of bis-carboxy DBI PTCA is approximately equal to 3.4 A.
  • the annealing step was carried out in vacuum or inert gas. It included two stages: 1) exposure of bis-carboxy DBI PTCA layer at 350 0 C for 30 minutes to carry out a partial pyro lysis of the organic compound with at least partial removal of the hetero-atomic groups and the substituents from the layer, and 2) fusion of the carbon-conjugated residues in the temperature range of 650 - 900 0 C for 10 - 300 minutes in order to form the predominantly planar graphene-like carbon-based structures.
  • the annealing regime is shown in Figure 4. At least part of the substituents S 1 , S 2 , S3 and S 4 and hetero-atomic groups have been removed from the solid layer.
  • Thickness of the bis-carboxy DBIPTCA layer after the drying stage was about 50 nm. After the annealing, thickness of the layer was decreased to about 70 % of the initial thickness. This value was essentially reproducible in the above referenced time and temperature ranges.
  • a thermo gravimetric analysis of the layer of bis-carboxy DBI PTCA is shown in Figure 5.
  • the formation of the layer of bis-carboxy DBI PTCA had three main stages: 1) water and ammonia removal from the solid precursor layer (24-250 0 C), 2) decarboxylation process (353-415°C), and 3) DBI PTCA layer partial pyrolysis with carbon-conjugated residues forming (541-717°C).
  • Formula weight (FW) of Bis(carboxybenzimidazoles) of PTCA is shown in Table 6.
  • FIG. 7 One possible graphene-like carbon-based structure is shown schematically in Figure 7.
  • the graphene-like structure comprises a substantially planar hexagonal carbon core (the carbon atoms are marked as black circles in Figure 7).
  • the hexagonal carbon core possesses high electrical conductivity which is close to the conductivity of metal.
  • Atoms of hydrogen (white circles in Figure 7) are positioned along the perimeter of graphene-like carbon-based structure.
  • Figure 8 schematically shows the anisotropic ribtan layer 3 on the substrate 2 after the annealing step.
  • Figure 12 shows Raman spectrum of the annealed samples.
  • the spectrum includes typical lines for sp 2 bonded carbon material.
  • the position of these line G) and its FWHM suggests that the metallic ribtan layer consists of a graphene-like layered structure.
  • Lines D and 2D are split which means that the surface of ribtan layers consist of edges of graphene- like layers. Detection of Raman spectra in different points of the sample proves homogeneity of phase composition and distribution of structural defects over ribtan surface (Figure 13).
  • resistivity There is some anisotropy of resistivity along graphene-like nanoribbons (per) which is lower than resistivity across the nanoribbons (par).
  • the resistivity strongly depends on fusion temperature and exposure time.
  • Figure 14 shows resistivity as a function of maximum annealing temperature (T max ) and
  • Figure 15 shows resistivity as a function of time of a sample exposure at maximum temperature.
  • resistivity decreases with increasing of time and temperature of fusion.
  • the resistivity perpendicular to the coating direction is about two - three times smaller than resistivity parallel to the coating direction.
  • the ribtan layer possesses anisotropy of resistivity.
  • anisotropy of the resistivity corresponds to a better charge transport in the direction along the graphene-like carbon-based structures.
  • the voltage-current characteristics obtained at different annealing temperatures on bis-carboxy DBIPTCA layer are shown in Figure 16.
  • the ribtan layers are characterized by dependence of conductivity (a reciprocal value of electrical resistivity) on annealing temperature and by transition: dielectric -semiconductor -conductor state.
  • the high value of the measured conductivity proves the global (continuous) character of the ribtan layer.
  • Example 2 This example describes the formation of another the electrical-conducting ribtan layer.
  • the ribtan layer was formed on a substrate on the basis of a mixture of 2-oxo-2,3- dihydro-l"H-l,2':r,2"-terbenzimidazoletricarboxylic acids and 2-oxo-2,3-dihydro-l'H-l,2'- bibenzimidazole-dicarboxylic acids.
  • the compounds correspond to the structures 60 and 61 of Table 6 and are shown in Figure 2.
  • the annealing step was carried out in vacuum at 65O 0 C for approximately 20 minutes.
  • the layer thickness dropped from approximately 100 nm to 60 nm.
  • the duration and temperature of this step were selected so as to ensure partial pyrolysis of the organic compound with formation of carbon-conjugated residues.
  • the substituents and the hetero- atomic groups have been at least partially removed from the solid layer.
  • the further annealing resulted in the formation of predominantly planar graphene-like carbon-based structures via thermal polymerization of the carbon-conjugated residues.
  • the graphene-like structure comprises substantially planar hexagonal carbon core (the carbon atoms are marked as black circles in Figure 7).
  • the hexagonal carbon core possesses high electric conductivity which approaches the conductivity of metals.
  • the annealing step was carried out in a hydrogen flow and the atoms of hydrogen (white circles in Figure 7) were positioned along the perimeter of graphene-like carbon-based structure.
  • Figure 16 shows schematically the anisotropic ribtan layer (3) on the substrate (2) after the annealing step, where the carbon-based structures have a homeotropic alignment.
  • Example 3 The example demonstrates a method of photolithographic patterning of ribtan layer.
  • the ribtan layer was formed as described in Example 1 or Example 2.
  • Figures 18-22 illustrate this embodiment of the present invention during various patterning steps.
  • the first step of patterning was formation of a HPR (positive) photoresist layer on the ribtan surface.
  • the ribtan layer on a substrate was placed in a clean room which was illuminated with yellow light, since photoresist is not sensitive to wavelengths higher than approximately 0.5 ⁇ m.
  • the ribtan sample was held on a vacuum spindle, and a liquid resist was applied to the center of the sample.
  • the structure was then rapidly accelerated up to a constant rotational speed 3000 rpm, which was maintained for 40 second.
  • Figure 18 schematically shows ribtan layer (3) on a substrate (2) coated by photoresist layer (4).
  • many variations may be used as methods of coating of samples with the photoresist layer, such as spray coating, flooding, electrostatic method, and any other methods known in the art.
  • the multilayer structure was exposed to a soft bake (at 100 0 C for 60 seconds) in order to remove the solvent from the photoresist layer and to increase adhesion of the photoresist to the ribtan layer.
  • the sample coated by photoresist layer was aligned with respect to the photomask in an optical lithographic system.
  • the photomask has a pattern corresponding to a desired functional structure, and the photoresist was exposed to UV light through the mask during 120 seconds, as shown in Figure 19.
  • Figure 19 schematically shows the multilayer structure comprising the substrate (2), the metallic ribtan layer (3), and the photoresist layer (4), and the mask (5).
  • the mask (5) includes first translucent or transparent regions (6), and second opaque regions (7).
  • the exposed photoresist relaxed in air at room temperature during about 1 minute.
  • photoresist was dissolved in the mixture of HPR developer with DI water (1 :3) during 70 seconds.
  • the developed structure was then rinsed the flow of DI water during about 3 minutes and dried in nitrogen flow.
  • Figure 20 shows the produced structure comprising the ribtan layer (3) and the patterned photoresist layer (8). The structure shown in Figure 20 was then put in oxygen plasma that provides etching of the ribtan layer (3).
  • Figure 21 shows the patterned ribtan layer (9) with a patterned photoresist layer (8). Then, the photoresist was dissolved in acetone, leaving in the ribtan layer (9) the pattern that was the same as the opaque regions (7) on the mask shown in Figure 19.
  • Example 4 describes a method of electron-beam projection lithographic patterning of ribtan layer.
  • Figures 23-27 illustrate this embodiment of the present invention with illustration of the various patterning steps.
  • the ribtan layer on a substrate was formed as described in Example 1 or Example 2, and as shown.
  • the ribtan layer on a substrate was held on a vacuum spindle, and a polymer electron resist was applied to the center of the multilayer structure.
  • the structure was then rapidly accelerated up to a constant rotational speed, which was maintained for about 40 seconds.
  • the spin speed was generally in the range of 1000 - 10000 rpm to coat a uniform electron resist layer 10 up to about 0.5 to 1 ⁇ m thick, as shown in Figure 23.
  • the positive electron resist was used that comprises poly-methyl methacrylate and poly-butene-1 sulfone.
  • the positive electron resist allows achievement of resolution of approximately 0.1 ⁇ m.
  • the multilayer structure was exposed to a soft bake (typically at approximately 90° - 12O 0 C for about 60 to 120 second) in order to increase an electron resist adhesion to the multilayer structure.
  • FIG. 24 schematically shows the SCALPEL-system which uses a scattering mask 11 to conduct the reduction projection lithography with a scanner.
  • the mask was uniformly illuminated by a parallel electron beam of approximately lOOkeV 12.
  • the scattering mask was comprised of a thin (100 - 150 nm), low-atomic- number layer 13, and a thin (30 - 60 nm), high-atomic-number patterned layer 14.
  • the scattering mask 11 was almost completely electron transparent at the energies used, contrast was generated by utilizing the difference in electron-scattering characteristics between the layer 13 and the patterned layer 14.
  • the layer 13 of low-atomic- number material scatters electrons weakly with small angles, whereas the patterned layer 14 of high-atomic-number scatters most electrons strongly with high angles.
  • a SCALPEL aperture 15 in the back- focal plane of the projection optics 16 blocks the strongly scattered electrons, forming a high-contrast pattern 17 on the electron resist layer 10.
  • Figure 25 shows the resulting structure comprising the ribtan layer on a substrate and the patterned electron resist layer 18.
  • the structure shown in Figure 25 was then put in oxygen plasma that provides etching of the ribtan layer 3.
  • Figure 26 shows the patterned ribtan layer (9) with patterned electron resist layer (18). Then the patterned electron resist layer 18 was removed. At last, the patterned ribtan layer 19 has been formed on the substrate 2, as shown in Figure 27.
  • Example 5 describes a method of extreme-ultraviolet lithographic patterning of ribtan layer.
  • Figure 28 illustrates this embodiment of the present invention.
  • the multilayer structure comprising a substrate 2 and a ribtan layer 3, and a photoresist layer 4 was formed as described in Example 1 or Example 2, resulting in the structure as shown in Figure 18.
  • FIG. 28 shows a schematic diagram of EUV lithographic system, comprising a source of extreme-ultraviolet radiation 20, a reflection mask 21, and a 4> ⁇ reduction camera 22.
  • the EUV radiation was reflected by the reflection mask 21 that was produced by patterning an absorber material deposited on the multilayer structure coated on the flat silicon plate.
  • the EUV radiation was reflected from the non-patterned regions of the reflected mask 21, passed through the 4> ⁇ reduction camera 22, and transferred the pattern into the photoresist layer 4 on the multilayer structure.
  • the subsequent steps of formation of a pattern in the ribtan layer were carried out as described by the Example 3.
  • Example 6 The example describes a method of transferring a pattern on a ribtan layer via imprint lithography.
  • the multilayer structure comprising a substrate 2 and a ribtan layer 3 was formed as described in Example 1 or Example 2.
  • the layer 23 made of an imprint resist was formed on the multilayer structure, as shown in Figure 29.
  • Thermal plastic materials were used as the imprint resists, and a suitable imprint temperature was chosen between about 70 0 C to 80 0 C above the material's glass transition temperature (Tg). This choice is explained by considering the typical deformation behavior of a thermal plastic polymer as a function of the temperature. At a temperature below Tg, the major contribution to the deformation comes from the elongation of the atomic distance, and the deformation is ideal elastic.
  • the Young's modulus for glassy polymers just below Tg is approximately constant over a wide range of polymers (3 x 10 9 Pa), and the magnitude of deformation is very small. Above Tg, local motion of chain segments takes place and the modulus of the material drops by several orders of magnitude. However, the entire chains are still fixed by the temporary network of entanglements. A rubber-elastic plateau region exists beyond Tg, where a relatively large deformation may occur due to extension of chain segments fixed between entanglement points. The modulus stays relatively constant in the rubbery state, and the deformation will recover after the force is released. Next is the rubbery flow region for linear amorphous polymers, but it does not occur for cross-linked polymers.
  • a hard mould 25 that contains features defined on its surface was used to emboss into the imprint resist layer 24 under controlled temperature and pressure conditions, as shown in Figures 30 and 31.
  • the features may have the nano-scale sizes.
  • the imprinting temperature was chosen to be Tg + 80 0 C and the applied pressure was 50 kg cm- 2 .
  • a very good pattern definition was reached.
  • a thickness contrast in the imprint resist layer 24 was formed, as shown in Figure 32.
  • This thickness contrast was further transferred through the imprint resist layer 24 via an O 2 plasma-based anisotropic etching process.
  • a patterned resist layer 26 has been formed, as shown in Figure 33.
  • a hard mould was made of silicon; other materials selected from the list comprising SiO 2 , SiC, silicon nitride, sapphire, and diamond may be used for making the mould.
  • the subsequent steps of formation of a pattern in the ribtan layer were carried out similarly to the Example 3, and as shown in Figures 21 and 22.
  • Example 7 illustrates another embodiment of the patterning method with use of thermal imprint lithography.
  • a layer comprising a water-based solution 27 of bis-carboxy DBI PTCA was applied on a substrate, as shown in Figure 34.
  • the solution comprised a mixture of six isomers, as shown in Figure 1.
  • Bis-carboxy DBI PTCA is a ⁇ -conjugated organic compound, where the predominantly planar carbon-conjugated core (CC in formula I) comprises rylene fragments, the benzimidazole groups serve as hetero-atomic groups, and carboxylic groups serve as substituents providing solubility.
  • the molecular structure provides for the formation of rod-like molecular stacks. Quartz was used as a substrate material.
  • a hard mould 25 with the features on its surface was used to emboss into wet layer 27 under controlled temperature and pressure conditions, as shown in Figures 35 and 36.
  • the features may be characterized with the nano-scale sizes.
  • the imprinting temperature was chosen to remove solvent from the wet layer 27 and to form a solid layer 28 having a thickness contrast, as shown in Figures 36 and 37. This thickness contrast was further transferred through the solid layer 28 with the O 2 plasma-based anisotropic etching process.
  • the next step was annealing which was carried out in vacuum at approximately 65O 0 C for about 20 minutes.
  • the duration and temperature of this step were selected so as to ensure partial pyrolysis of the organic compound with at least partial removing of substituents, hetero-atomic and solubility groups from the solid patterned layer, and forming predominantly planar graphene-like carbon-based structures on the basis of the carbon- conjugated residues.
  • the patterned ribtan layer 29 has been formed on the substrate 2 as the result of annealing, as shown in Figure 38.
  • Example 8 illustrates another embodiment of the patterning method with use of reverse imprint lithography. If the mould feature has a high aspect ratio, then a different mode may be used for the forming of the patterns in the ribtan layer.
  • the features may be of the nano-scale sizes.
  • a layer of the water-based solution 30 of bis-carboxy DBI PTCA was applied on the mould surface that contains nanoscale features, as shown in Figure 39.
  • the solution comprised a mixture of six isomers as shown in Figure 1.
  • Bis-carboxy DBI PTCA is a ⁇ - conjugated organic compound, where the predominantly planar carbon-conjugated core (CC as in formula I) comprises rylene fragments, the benzimidazole groups serve as hetero- atomic groups and carboxylic groups serve as substituents providing solubility.
  • the molecular structure provides for the formation of rod-like molecular stacks. In this case, the layer of water-based solution 30 cannot planarize the mould surface, leaving undulations on the surface of the wet layer coated on the surface (see Figure 39).
  • duration and temperature of this step were selected so as to ensure partial pyro lysis of the organic compound with at least partial removing of substituents and hetero-atomic from the ribtan layer, and forming predominantly planar graphene-like carbon-based structures on the basis of the carbon- conjugated residues.
  • the example illustrates another embodiment of the patterning method with use of imprint lithography.
  • a layer of a water-based solution of bis-carboxy DBI PTCA was applied on a substrate 2.
  • the solution comprised a mixture of six isomers as shown in Figure 1.
  • Bis-carboxy DBI PTCA is a ⁇ -conjugated organic compound, where the predominantly planar carbon-conjugated core (CC in formula I) comprises rylene fragments, the benzimidazole groups serve as hetero-atomic groups and carboxylic groups serve as substituents providing solubility.
  • the molecular structure provides for the formation of rod- like molecular stacks. Quartz was used as a substrate material.
  • the drying step was performed at room temperature and humidity of around 70%. By the end of the drying step, the produced solid layer 32 usually retains about 10% of the solvent (see Figure 43).
  • a preheated mould 33 was brought into a contact with the surface of the solid layer 32, as shown in Figure 44, or into a close proximity with the surface.
  • the hard mould 33 contains features defined on its surface. The features may be characterized by the nano-scale sizes.
  • the mould was heated up by the spiral heater 35 controlled by DC, AC or pulsed voltage, as shown in Figure 45.
  • the heat from the mould caused local annealing of the ribtan material.
  • the mould temperature was selected such to provide annealing of parts 34 of the solid layer 32, which were in contact with tops of the mould protrusions.
  • the pattern to be transferred onto a multilayer structure was formed on one surface of a block of electroconductive material forming the mould 33, and with the features on its surface. The mould was brought into contact with the surface of the multilayer structure or into close proximity with the surface, as shown in Figure 46.
  • An electrode 36 was placed on the surface opposite to the multilayer structure.
  • the local heating and annealing could also be done with an electroconductive probe or array of probes, and optionally with an e-beam.
  • duration and temperature of this step were selected so as to ensure partial pyrolysis of the organic compound with at least partial removal of substituents, and hetero-atomic groups from the parts 34 of the solid layer 32, forming predominantly planar graphene-like carbon-based structures on the basis of the carbon-conjugated residues.
  • the patterned ribtan layer 37 has been formed on the substrate 2 as a result of annealing, as shown in Figure 47.
  • Example 10 illustrates one embodiment of an integrated circuit made with the ribtan layer according to the present invention.
  • Figures 48a and 48b show several simple integrated circuits which may be made by patterning of the ribtan layer, and having a source electrode 42 and a drain electrode 43, which are interconnected with a graphene-like carbon-based strip 44, which may be a graphene-like strip of nano-scale thickness.
  • Figure 48a shows an integrated circuit made by one of the lithographic methods disclosed in the present invention.
  • Figure 48b shows an integrated circuit made by one of thermal patterning methods disclosed in the present invention, wherein the area 45 was not exposed to a local annealing.
  • Example 11 illustrates another embodiment of the integrated circuit made with the ribtan layer according to the present invention.
  • Figures 49 (a, b) and 50 (a, b) show transistors which may be made by patterning of the ribtan layer, and having a source electrode 42 and a drain electrode 43, which are interconnected with a graphene-like carbon-based strip 44.
  • the transistors may be made by disposing a gate 46 adjacent to the graphene-like carbon-based strip 44 so that the electron transport property of the graphene-like carbon-based strip 44 is changed when a bias voltage is applied to the gate so as to induce an electric field that interacts with the graphene-like carbon-based strip 44.
  • Figures 49a and 50a show transistors made by one of the lithographic methods disclosed in the present invention. These transistors were formed on the dielectric substrate 2.
  • Figures 49b and 50b show transistors made by one of the thermal patterning methods disclosed in the present invention, wherein the area 45 was not exposed to a local annealing.
  • Example 12 illustrates another embodiment of the integrated circuit made with the ribtan layer according to the present invention.
  • Figures 51a and 51b show directional couplers, each of which has one input electrode 47 and two output electrodes 48 and 49.
  • the directional couplers were formed on a dielectric substrate 2.
  • Figure 51a shows the directional coupler made by one of the lithographic methods disclosed by the present invention.
  • Figure 51b shows directional coupler made by one of thermal patterning methods disclosed in the present invention, wherein the area 45 was not exposed to a local annealing.
  • FIGS 52a and 52b show interferometer configurations which may be made by patterning of the ribtan layer.
  • the interferometer configurations have a source electrode 50 and a drain electrode 51 which are interconnected with a loop-like structure that has a first branch 52 and a spaced-apart second branch 53.
  • a gate electrode 54 is disposed adjacent to the first branch 52 so that it is capable of exerting an electrical field substantially only on the first branch 52.
  • the interference may be registered by a change in the source-to-drain current.
  • the interferometer configurations were formed on the dielectric substrate 2.
  • Figure 52a shows interferometer configuration made by one of the lithographic methods disclosed in the present invention.
  • Figure 52b shows interferometer configuration made by one of the thermal patterning methods disclosed in the present invention, wherein the area 45 was not exposed to a local annealing.
  • FIGS 53a and 53b show multi-gate interferometer configurations which may be made by patterning of the ribtan layer.
  • the multi-gate interferometer configurations have a source electrode 55 and a drain electrode 56 which are interconnected with a loop-like structure that has a first branch 57 and a spaced- apart second branch 58.
  • Several gate electrodes 59, 60, and 61 are disposed adjacent to the first branch 57 so that they are capable of exerting an electrical field substantially only on the first branch 57.
  • the interference may be registered by the change in the source-to-drain current.
  • the multi-gate interferometer configurations were formed on the dielectric substrate 2.
  • Figure 53a shows multi-gate interferometer configuration made by one of the lithographic methods disclosed by the present invention.
  • Figure 53b shows multi-gate interferometer configuration made by one of thermal patterning methods disclosed by the present invention, where the area 45 was not exposed to a local annealing.
  • This example describes a method of formation of the multilayer structure with two ribtan layers patterned by the disclosed methods.
  • the multilayer structure comprising substrate 65 and ribtan layer 66 with an additional layer of silicon dioxide 67 was formed as described in Example 1 or Example 2, as shown in Figure 54.
  • Figures 54-72 illustrate this embodiment of the present invention during various patterning steps.
  • the first step of the patterning was formation of a resist layer on the multilayer structure.
  • the multilayer structure was placed in a clean room, which was illuminated with yellow light, since photoresist is not sensitive to wavelengths greater than approximately 0.5 ⁇ m. To ensure satisfactory adhesion of the resist the surface of the multilayer structure was pre-treated. The treatment has changed the surface of the multilayer structure from hydrophilic to hydrophobic.
  • a positive resist was used for the pattern formation step.
  • the multilayer structure was exposed to a soft bake (at approximately 90° - 12O 0 C for 60 - 120 second) in order to remove the solvent from the photoresist layer and to increase adhesion of the photoresist to the multilayer structure.
  • the multilayer structure coated by the photoresist layer was aligned with respect to the mask in an optical lithographic system.
  • the mask has a pattern corresponding to a desired functional structure, and the photoresist was exposed to UV light through the mask, as shown in Figure 56.
  • Figure 56 shows schematically the multilayer structure comprising the substrate 65, the ribtan layer 66, and the silicon dioxide layer 67, the photoresist layer
  • the mask 69 comprises the translucent or transparent regions 71, and the opaque regions 70.
  • the exposed photoresist was dissolved in the developer.
  • the photoresist development was done by flooding the exposed structure with the developer solution.
  • the developed structure was then rinsed and dried.
  • a post-baking at approximately 100° - 18O 0 C was conducted in order to increase the adhesion of the patterned photoresist layer to the multilayer structure.
  • Figure 57 shows the resulting structure comprising the multilayer structure and patterned photoresist layer 72.
  • the structure shown in Figure 57 was then put in an environment that provides etching of the exposed additional layer of silicon dioxide 67 but does not attack the patterned photoresist 72.
  • Figure 58 shows the multilayer structure with patterned additional layer of silicon dioxide 73. After that the photoresist was stripped (see Figure 59).
  • the patterned additional layer of silicon dioxide 73 has been used as a mask for the subsequent processing.
  • Figure 59 was then put in an environment that provides etching of the exposed ribtan layer but does not attack the patterned additional layer of silicon dioxide 73 and the areas of ribtan layer covered by the patterned layer 73, as shown in Figure 60.
  • the next step of the patterning was a formation of the second resist layer 75 on the formed structure as shown in Figure 61.
  • the multilayer structure coated by the second photoresist layer 75 was aligned with respect to the mask in an optical lithographic system.
  • the mask had a pattern corresponding to a desired functional structure, and the photoresist was exposed to UV light through the mask, as shown in Figure 62.
  • Figure 62 shows schematically the multilayer structure comprising the substrate 65, the patterned ribtan layer 74, and the patterned silicon dioxide layer 73, the photoresist layer 75, and the mask.
  • the mask comprises the first translucent or transparent regions 78, and the second opaque regions 77.
  • the exposed photoresist was dissolved in the developer.
  • the photoresist development was done by flooding the exposed structure with the developer solution.
  • the developed structure was then rinsed and dried. After the development step, a post-baking at approximately 100° - 18O 0 C was conducted in order to increase the adhesion of the patterned photoresist layer to the multilayer structure.
  • Figure 63 shows the resulting structure comprising the multilayer structure and the patterned photoresist layer 79.
  • the structure shown in Figure 63 was then put in an environment that provides etching of the exposed patterned additional layer of silicon dioxide 73 but does not attack the patterned photoresist 79.
  • Figure 64 shows the multilayer structure with the additionally patterned layer of silicon dioxide 80. After that the photoresist was stripped, as shown in Figure 65.
  • the following step of the patterning was a formation of the third resist layer 81 on the formed structure as shown in Figure 66.
  • the multilayer structure coated by the third photoresist layer 81 was aligned with respect to the mask in an optical lithographic system.
  • the mask had a pattern corresponding to a desired functional structure, and the photoresist was exposed to UV light through the mask 82, as shown in Figure 67.
  • Figure 67 schematically shows the multilayer structure comprising the substrate 65, the patterned ribtan layer 74, and the twice patterned silicon dioxide layer 80, the photoresist layer 81, and the mask 82.
  • the mask 82 comprised the first translucent or transparent regions 84, and the opaque regions 83.
  • the exposed photoresist was dissolved in the developer.
  • the photoresist development was done by flooding the exposed structure with the developer solution.
  • the developed structure was then rinsed and dried.
  • FIG. 68 shows the resulting structure comprising the multilayer structure and the patterned third photoresist layer 81 with the opened windows 82.
  • a wet layer 83 comprising a water-based solution of bis-carboxy DBI PTCA was applied on the formed structure, as shown in Figure 69.
  • the wet layer was dried.
  • Figure 70 shows the dried layer 84 located on the top of the multilayer structure.
  • the patterned dried layer 85 has been formed, as shown in Figure 71.
  • the next step was annealing of the dried patterned layer 85 which was carried out in vacuum at approximately 65O 0 C for about 20 minutes.
  • the duration and temperature of this step were selected so as to ensure partial pyrolysis of the organic compound with at least partial removal of substituents and hetero-atomic groups from the solid patterned layer, forming predominantly planar graphene-like carbon-based structures on the basis of the carbon- conjugated residues.
  • the patterned ribtan layer 86 on the formed structure has been formed as the result of annealing, as shown in Figure 72.
  • Example 16 The example describes synthesis of bis(carboxybenzimidazoles) of perylene tetracarboxylic acid (rylene fragments ## 4 and 5 in Table 1):
  • Precipitate was filtered and rinsed with hot water (1 L). Filter cake was agitated in a 2% solution of hydrogen chloride for 1 hour at 90 0 C. Precipitate was filtered and rinsed with hot water (1 L) and dried at 100 0 C. Yield 38.3 g.
  • Example 18 The example describes synthesis of dicarboxymetylimide of perylentetracarboxylic acid (carboxylic acid of base rylene fragment 10 in the Table 1)
  • Example 19 The example describes synthesis of violanthrone disulfonic acid (anthrone fragment
  • Violanthrone (10 g) was added to chlorosulfonic acid (50 ml) at ambient conditions. Then reaction mass was agitated at 85-90 0 C for 15 hours. After self cooling a reaction mass was added by parts into water (600 ml). Precipitate was filtered and rinsed with water until filtrate became colored. Filter cake was agitated in the boiling water (500 ml) for two hours. The product was precipitated by addition of concentrated hydrochloric acid (600 ml). Precipitate was filtered, washed with 6 N hydrochloric acid (200 ml) and dried in oven ( ⁇ 100°C). Yield 11.8 g.
  • Example 20 The example describes synthesis of isoiolanthrone disulfonic acid (anthrone fragment # 25 in Table 2):
  • decacyclene polycyclic hydrocarbon fragment # 33 in Table 3
  • Cooled suspension was diluted with isopropanol (400 ml) and a precipitate was filtered.
  • Filter cake was suspended in hot N-methylpyrrolidone (400 ml, ⁇ 150°C). Cooled suspension was filtered.
  • Filtrate was diluted with water (1.5 L). Obtained precipitate was filtered, rinsed with water and dried at ⁇ 100°C. 11.2 g of dry powder were prepared.
  • Filtrate (N-methylpyrrolidone - isopropanol) was diluted with water (1 L). Precipitate was filtered, rinsed with water and dried at ⁇ 100°C. 1.18 g of dry powder was prepared.
  • Obtained powder was combined and agitated in a boiling tetrachloroethane (70 ml) for 2 hours. Cooled suspension was filtered. Filter cake was rinsed with tetrachloroethane and chloroform.
  • the example describes synthesis of decacyclene trisulfonic acid (polycyclic hydrocarbon fragment # 33 in Table 3):
  • Decacyclene (1 g) was charged into chlorosulfonic acid (5 ml) at ambient conditions. During charging hydrogen chloride was liberating. Then reaction mass was agitated at the room temperature for 48 hours. Then reaction mass was added into water (50 ml) by portions. Precipitate was filtered. Filter cake was agitated in water (100 ml) at ambient conditions and in hot water (80 0 C) for 2 hours. Prepared solution was filtered through fiber glass filter. Filtrate was diluted with concentrated hydrochloric acid (100 ml) and dried at ⁇ 100°C. Yield 1.13 g.
  • Example describes preparation of N,N'-(l-undecyl)dodecyl-5,l l-dihexylcoronene- 2,3:8,9-tetracarboxydiimide (coronene fragment 49 in the Table 4).
  • the preparation comprised 6 steps:
  • N,N'-Dicyclohexyl- 1 ,7-dibromoperylene-3 ,4:9,10-tetracarboxydiimide was synthesized by the reaction of l,7-dibromoperylene-3,4:9,10-tetracarboxylic dianhydride (30.0 g) with cyclohexylamine (18.6 mL) in N-methylpyrrolidone (390 mL) at ⁇ 85 ° C.
  • N,N'-Dicyclohexyl- 1 ,7-di(oct- 1 -ynyl)perylene-3 ,4:9,10-tetracarboxydiimide was synthesized by Sonagashira reaction: N,N'-dicyclohexyl-l,7-dibromperylene-3,4:9,10- tetracarboxydiimide (24.7 g) and octyne-1 (15.2 g) in the presence of bis(triphenylphosphine)palladium(II) chloride (2.42 g), triphenylphospine (0.9 g),and copper(I) iodide (0.66 g).
  • N,N'-dicyclohexyl-5,l l-dihexylcoronene-2,3:8,9-tetracarboxydiimide was synthesized by the heating of N,N'-dicyclohexyl-l,7-di(oct-l-ynyl)perylene-3,4:9,10- tetracarboxydiimide (7.7 g) in toluene (400 mL) in the presence of 1,8-diazabicyclo [5.4.0]undec-7-ene (0.6 ml) at 100-110° C for 20 hours.
  • N,N'-( 1 -undecyl)dodecyl-5 , 11 -dihexylcoronene-2,3 : 8,9-tetracarboxydiimide was synthesized by the reaction of 5,l l-di(hexyl)coronene-2,3:8,9-tetracarboxylic dianhydride with 12-tricosanamine.
  • reaction mixture was mixed with acetic acid (5 mL), centrifuged, solid was dissolved in chloroform (0.5 mL) which was washed with water and dried over sodium sulfate.
  • Thin layer chromatography probe showed good formation of product with Rf 0.9 (eluent: chloroform-hexane-ethylacetate-methanol (100:50:0.3:0.1 by V)).
  • the reaction mixture was added in small portions to acetic acid (500 mL) with simultaneous shaking.
  • the orange-red suspension was kept for 3 hours with periodic shaking, then filtered off.
  • the filter cake was washed with water (0.5 L), and then was shaken with water (0.5 L) and chloroform (250 mL) in a separator funnel.
  • the organic layer was separated, washed with water (2x350 mL) and dried over sodium sulfate overnight.
  • the evaporation resulted in 7.0 g of crude product.
  • Column chromatography was carried out using exactly tuned eluent mixture: chloroform (700 mL), petroleum ether (2 L), ethylacetate (0.6 mL) and methanol (0.2).

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Abstract

The present invention relates generally to the field of integrated electronics. More specifically, the present invention relates to patterned graphene-like carbon-based integrated circuits and methods of production thereof. Methods of photo-, electron-beam projection, extreme-ultraviolet, and imprint lithographic patterning and also several thermal patterning methods are disclosed in the present invention.

Description

PATTERNED INTEGRATED CIRCUIT AND METHOD OF PRODUCTION THEREOF
FIELD OF THE INVENTION
The present invention relates to patterned graphene-like carbon-based integrated circuits macro- and micro-electronics and methods for production thereof.
BACKGROUND OF THE INVENTION In modern integrated electronics technology, a silicon wafer is lithographically patterned to form a large number of interconnected electronic components (transistors, resistors, capacitors, etc) and arrays of thin film transistors for flat panel displays. The technology is built upon the semiconducting properties of silicon and on lithographic patterning methods. Increasing the density of electronic components and reducing the power consumption per component are two of the most important objectives in the microelectronics industry. These objectives have driven the steady advance in manufacturing technology and reduction in the size of the components over the past decades. However, miniaturization of silicon-based electronics will reach an ultimate limit in the near future, primarily because of limitations imposed by the material properties of silicon and doped silicon, at the nanoscale. To sustain the current trend in microelectronics beyond the limits imposed by silicon-based microelectronics technologies, alternative technologies need to be developed. Requirements for such an alternative technology include smaller feature sizes than feasible with silicon-based microelectronics, more energy- efficient electronics strategies, and production processes that allow large-scale integration, preferably using lithographic patterning methods related to those used in silicon-based microelectronics fabrication.
Several alternatives to silicon-based electronics have been proposed. However, none of the proposed alternatives fulfills all three of the above-listed requirements.
Molecular electronics is considered to be an attractive alternative to the silicon- based electronics. Molecular electronics utilizes molecular building blocks for the fabrication of electronic components. Carbon nanotubes are considered to be particularly attractive candidates for the building blocks of molecular electronics. Carbon nanotubes are essentially graphite tubes comprising several (one to over 100) graphene layers in tubular configurations. A graphene layer consists of a single layer of sp2 carbon atoms arranged in a hexagonal pattern with each atom (except those at the edges) chemically connected to its three neighbors. Crystalline graphite consists of the stacked graphene layers.
The electronic transport properties of carbon nanotubes are defined by the π-bands of the graphene network. Hence, the electronic properties are directly related to their graphitic structure. Nanotubes conduct electrons in either a metallic mode or semiconducting mode depending on their specific structure. They have been found to be one-dimensional ballistic conductors over micron-scale distances at room temperature. The bandgap of semiconducting nanotubes depends on the diameter of the nanotube, hence it can be tuned by adjusting the diameter. Nanotubes can sustain very large currents (up to 1 mA), and sp2-sp2 carbon bond ranks among the strongest in nature, making nanotubes exceptionally stable compared to other molecules. In addition, nanotubes have been demonstrated to be capable of forming field-effect transistors and small integrated circuits, involving up to three carbon nanotubes. These structures consist of several carbon nanotubes which are deposited on an insulating substrate and interconnected with metal wires that are lithographically patterned on top of the nanotubes.
However there are important disadvantages associated with carbon nanotube-based molecular electronics. For example, since the conductive properties of nanotubes (e.g., metallic versus semiconducting) are determined by the diameter of the tubes, they must be pre-selected before they are positioned on the substrate; there are no means developed right now to control a manufacturing process for the large-scale integration of nanotubes. Also, present nanotube configurations are interconnected with metal wires. The ohmic resistance at each metal-to-nanotube contact is quite large. For example, in the "on" state, each carbon nanotube transistor exhibits a resistance of several kilo Ohms, mostly due to the resistance of the metal-nanotube contact. This means that in comparison with silicon transistors relatively large amounts of heat are dissipated at the contacts.
These disadvantages demonstrate why nanotubes are not used yet in commercial integrated electronic circuits, and integration of carbon nanotube-based electronic devices on a large scale is not expected to be feasible in the foreseeable future.
Therefore, there is a need for electronic device technologies that allow ballistic electron transport at room temperature and that do not exhibit high device-interconnect resistance. The present invention provides patterned graphene-like carbon-based integrated circuits and methods of production thereof - which overcome the above mentioned drawbacks of conventional, silicon-based integrated circuits and alternative molecular electronics technologies.
SUMMARY OF THE INVENTION The present invention provides a method of lithography patterning, comprising: a) formation of a ribtan layer, comprising the sequence of following steps:
(i) application of a solution on a substrate, wherein the solution comprises at least one π-conjugated organic compound of a general structural formula I or any combination thereof:
where CC is a predominantly planar carbon-conjugated core; A is a hetero-atomic group; p is O, 1, 2, 3, 4, 5, 6, 7, or 8; S1, S2, S3 and S4 are substituents, ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8; and sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8; (ii) drying with formation of a solid precursor layer; and
(iii) annealing with formation of a ribtan layer comprising graphene-like carbon- based structures, wherein said annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of the hetero-atomic groups and the substituents from the layer, and 2) fusion of the carbon- conjugated residues in order to form the predominantly planar graphene-like carbon-based structures; and b) formation of a pattern in the multilayer structure by one of lithographic methods, comprising the sequence of following steps: (iv) formation of a resist layer on the multilayer structure;
(v) formation of a pattern in the resist layer; and
(vi) transfer of the pattern from the resist layer to the multilayer structure.
In a further aspect, the present invention provides a method of thermal patterning, comprising the following steps:
- application of a solution on a substrate,
wherein the solution comprising at least one π-conjugated organic compound of a general structural formula I or a combination of the organic compounds of the general structural formula I:
where CC is a predominantly planar carbon-conjugated core; A is a hetero-atomic group; p is 0, 1, 2, 3, 4, 5, 6, 7, or 8; S1, S2, S3 and S4 are substituent; ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8; and sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8; - drying with formation of a solid precursor layer, and - formation of a pattern in the solid precursor layer by a local annealing, wherein said local annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of the hetero-atomic groups and the substituents from the solid layer and 2) fusion of the carbon-conjugated residues in order to form the predominantly planar graphene-like carbon-based structures.
In still further aspect, the present invention provides a method of direct lithographic patterning, comprising the sequence of following steps: - depositing a wet pattern on a substrate using a solution which comprises at least one π- conjugated organic compound of the general structural formula I or a combination of the organic compounds of the general structural formula I:
where CC is a predominantly planar carbon-conjugated core; A is a hetero-atomic group; p is 0, 1, 2, 3, 4, 5, 6, 7, or 8; Si, S2, S3 and S4 are substituent; ml, ml, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8; and sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8;
- drying of said wet pattern with the formation of a solid pattern, and
- annealing with the formation of a solid pattern comprising graphene-like carbon-based structures and possessing electrical-conductivity, wherein said annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of hetero-atomic groups and substituents from the solid pattern and 2) fusion of the carbon-conjugated residues in order to form the predominantly planar graphene-like carbon-based structures.
In yet further aspect, the present invention provides an integrated circuit, comprising a ribtan layer on the substrate, wherein the ribtan layer is patterned to define at least one functional structure, wherein the method of patterning is any of the methods of patterning disclosed in the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
These and various other features and advantages of the present invention will become better understood upon reading of the following detailed description in conjunction with the accompanying drawings and the appended claims provided below, where: Figure 1 shows chemical formulas of six isomers of Bis (carboxybenzimidazoles) of Perylenetetracarboxylic acids;
Figure 2 shows chemical formulas of mixture of 2-oxo-2,3-dihydro-l"H-l,2':r,2"- terbenzimidazoletricarboxylic acids and 2-oxo-2,3-dihydro-l'H-l,2'-bibenzimidazole- dicarboxylic acids;
Figure 3 schematically shows the disclosed ribtan layer after the drying step, wherein the planes of π-conjugated organic compound are oriented predominantly perpendicularly to the substrate surface;
Figure 4 shows the typical annealing regime disclosed; Figure 5 shows the results of thermo-gravimetric analysis of the bis-carboxy DBI
PTCA layer;
Figure 6 schematically shows the disclosed ribtan layer after the pyrolysis of the organic compound, wherein the planes of carbon-conjugated residues are oriented predominantly perpendicularly to the substrate surface; Figure 7 schematically shows a graphene-like carbon-based structure;
Figure 8 schematically shows an embodiment of the disclosed ribtan layer, wherein the planes of graphene-like carbon-based structures are oriented predominantly perpendicularly to the substrate surface;
Figure 9 shows TEM image of bis-carboxy DBIPTCA annealed at 650 0C for 30 minutes;
Figure 10 shows electron diffraction on bis-carboxy DBIPTCA ribtan layer annealed at 650 0C for 30 minutes;
Figure 11 shows absorption spectra of the annealed and dried layer of bis-carboxy DBI PTCA; Figure 12 shows Raman spectra of the annealed samples;
Figure 13 shows Raman spectra at different points of the sample;
Figures 14 shows resistivity as a function of maximum annealing temperature
(, 1 max,)?
Figure 15 shows resistivity as a function of time of a sample exposure at maximum temperature; Figure 16 shows the voltage-current characteristics obtained at different annealing temperatures on bis-carboxy DBIPTCA layer;
Figure 17 schematically shows an embodiment of the disclosed ribtan layer, wherein the planes of graphene-like carbon-based structures are oriented predominantly parallel to the substrate surface;
Figures 18-22 schematically show a series of process steps of photolithographic patterning of ribtan layer according to the present invention;
Figures 23-27 schematically show a series of process steps of electron-beam projection lithographic patterning of ribtan layer according to the present invention; Figure 28 shows a schematic diagram of EUV lithographic system used for an extreme-ultraviolet lithographic patterning of ribtan layer according to the present invention;
Figures 29-33 schematically show a series of process steps of one embodiment of an imprint patterning of ribtan layer according to the present invention; Figures 34-38 schematically show a series of process steps of another embodiment of a thermal imprint patterning of ribtan layer according to the present invention;
Figures 39-42 schematically show a series of process steps of another embodiment of a reverse imprint patterning of ribtan layer according to the present invention;
Figures 43-47 schematically show a series of process steps of another embodiment of an imprint patterning of ribtan layer according to the present invention;
Figures 48-53 schematically show top views of an integrated circuit according to the present invention; and
Figures 54-72 illustrate a method of formation of a multilayer structure with two ribtan layers patterned by disclosed methods.
DETAILED DESCRIPTION OF THE INVENTION
The general description of the present invention having been made, a further understanding can be obtained by reference to the specific embodiments, which are given herein only for the purpose of illustration and are not intended to limit the scope of the appended claims. Hereinafter the name ribtan material is used for a new material disclosed. Ribtan is a carbon material which can exist in two modification: 1) it can consist of aligned graphene- like nanoribbons which are aligned parallel to each other and perpendicular (edge-on) to surface of substrate, and 2) it can consist of aligned graphene-like sheets which are aligned parallel to each other and parallel (face-on or homeotropic) to the surface of substrate. Graphene-like nanoribbons are narrow strips of graphene - one-atom-thick planar sheet of sp2-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. Graphene- like sheets are wide sheets of graphene - one-atom-thick planar sheet of sp2-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. The layers made of ribtan will be hereinafter named as ribtan layers. Technology of ribtan layers production will be hereinafter named ribtan technology. The ribtan technology is based on a thermally induced carbonization of organic compounds with predominantly planar carbon-conjugated cores.
Ribtan technology comprises a sequence of technological steps. The first step in ribtan technology is cascade crystallization process. Cascade crystallization is a method of the consecutive multi-step crystallization process for production of the solid precursor layers with ordered structure. The process involves a chemical modification step and several steps of ordering during the formation of the solid precursor layer. The chemical modification step introduces hydrophilic groups on the periphery of the molecule in order to impart amphiphilic properties to the molecule. Amphiphilic molecules stack together into supramolecules. The specific concentration is chosen, at which supramolecules are converted into a liquid-crystalline state to form a lyotropic liquid crystal (LLC), which is the next step of ordering. The LLC is deposited under the action of a shear force onto a substrate, so that the shear force direction determines the crystal axis direction in the resulting solid precursor layer. This shear-force - assisted directional deposition is the next step of ordering, representing the global ordering of the crystalline or polycrystalline structure on the substrate surface. The last step of the process is drying/crystallization, which converts the lyotropic liquid crystal into a solid precursor layer with highly ordered molecular structure. Planes of π-conjugated molecules in the formed precursor layer can be aligned parallel (face-on or homeotropic) or perpendicular (edge-on) to the surface of substrate depending on molecular structure and /or coating technique. Control over the precursor layer structure allows formation of layers comprising continuous graphene-like nanoribbons or graphene-like sheets with high electron mobility and low resistivity during carbonization process. Cascade crystallization is followed by carbonization process named hereinafter as a step of formation of the metallic ribtan layer. Carbonization is the term for a set of conversion reaction of an organic substance into carbon. Carbonization is usually a heating cycle. Carbonization might be performed with a heater such as a radiating heater, resistive heater, heater using an ac-electric or magnetic field, heater using a flow of heated liquid, and heater using a flow of heated gas. Carbonization is performed in a reducing or inert atmosphere with a simultaneous slow heating, over a range of temperature that varies with the nature of the particular precursor and may extend to 2500 0C. Carbonization is usually a complex process and several reactions may take place sequentially or simultaneously such as pyro lysis and fusion. Also carbonization process may be enhanced by addition of gas- phase or liquid-phase catalyst or reagents.
The first stage of carbonization is a pyrolysis process. Pyrolysis is the chemical decomposition of a condensed substance. Common products of pyrolysis are volatile compounds containing non-carbon atoms and solid carbon residue. Preferably the diffusion of the volatile compounds to the atmosphere occurs slowly to avoid disruption and rupture of the carbon network. As a result, carbonization is usually a slow process. Its duration may vary considerably depending on the composition of the end-product, type of precursor, thickness of the material, and other factors. Pyrolysis process converts the solid precursor layer into essentially all carbon (product of pyrolysis). The second stage of carbonization is a fusion reaction. Fusion (in other words condensation or polymerization) in ribtan technology is chemical reactions between neighboring molecules or their pyrolized residues and which lead to growth of continuous graphene-like nanoribbons (in case of edge-on orientation of molecules in precursor layer) or stacked graphene-like sheets (in case of homeotropic precursor layer). Several intermediate materials are formed during carbonization process. Product of pyrolysis consists of carbon cores separated by gaps. All structural parameters of the pyrolysis product (interplanar spacing; structure of residual carbon cores; dimensions of gaps between residual carbon cores and their concentration; orientation of carbon cores in respect to the substrate surface) are determined by structure of a precursor layer. Fusion process of product of pyrolysis leads to formation of an array of graphene-like nanoribbons or stacked graphene-like sheets with gaps. Generally, atomic structure of the nanoribbons or sheets with gaps is similar to the product of pyrolysis, but islands of sp2 carbon atoms grow and get ribbon-like or sheet-like morphology. Structural parameters of the nanoribbons or sheets with gaps such as structure of residual carbon cores, dimensions of gaps between residual carbon cores and their concentration - are determined by parameters of carbonization process including but not limited to temperature, time, composition and pressure of ambient gas. Interplanar spacing and orientation of carbon cores in respect to the substrate surface depends on structure of precursor layer. The intermediate materials described above have different electronic properties, especially conductivity. Mobility of charge carriers within graphene-like nanoribbon or graphene-like sheet reaches high values, which are approximately equal to 2*105 Cm2V1S"1. Mobile charge carriers overcome the gaps between the graphene-like nanoribbons by hopping, and this conductivity is named hopping conductivity. Electrical properties of the intermediate material depend on the concentration of gaps in the graphene-like nanoribbons or graphene-like sheets. Larger concentration of gaps leads to a smaller total electrical conductivity of the layer. By controlling the concentration of gaps, the layers can be formed in any of three states: insulating, semiconducting and metallic. The semiconducting state and the metallic state can be characterized as electrical-conducting states. In the insulating state the material has resistivity in the range of 108Ω*cm to 1018Ω*cm. In the semiconducting state, the resistivity of the material is in the range of lO^Ω^cm to 108Ω*cm.
In the metallic state, the resistivity of the material is in the range of 10~6Ω*cm to lO^Ω^cm.
There is no energy gap in the energy band structure of the graphene-like sheet. One possible method of creating an energy gap is the formation of thin graphene-like nanoribbons. The width of these graphene-like nanoribbons is selected so as to control the energy gap in electron energy distribution spectrum that is formed due to quantum- dimensional effects. Formation of the ordered graphene-like nanoribbons by fusion reaction in the ribtan structure allows precise control of a nanoribbon width simply by controlling the layer thickness. The precursor layer thickness depends only on solution concentration and coating parameters for layers obtained from LLC solution.
The ribtan technology allows the high volume production of ribtan layers over large surface (from several square millimeters to several square meters or larger). It allows low- cost manufacturing of the ribtan material for a broad range of different electronic devices, including integrated circuits.
In a first preferred embodiment, the present invention provides a method of lithography patterning, comprising: a) formation of a ribtan layer, comprising the sequence of following steps: (i) application of a solution on a substrate, wherein the solution comprises at least one π-conjugated organic compound of a general structural formula I or any combination thereof:
where CC is a predominantly planar carbon-conjugated core; A is a hetero-atomic group; p is 0, 1, 2, 3, 4, 5, 6, 7, or 8; Si, S2, S3 and S4 are substituents; ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8; and sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8; (ii) drying; and (iii) annealing with formation of a layer comprising graphene-like carbon-based structures, wherein said annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of the hetero-atomic groups and the substituents from the layer, and 2) fusion of the carbon-conjugated residues in order to form the predominantly planar graphene-like carbon- based structures; and b) formation of a pattern in the multilayer structure by one of lithographic methods, comprising the sequence of following steps: (iv) formation of a resist layer on the multilayer structure; (v) formation of a pattern in the resist layer; and (vi) transfer of the pattern from the resist layer to the multilayer structure.
In one embodiment of the disclosed method, the step of the electrical-conducting ribtan layer formation further comprises a formation of at least one additional layer. In another embodiment of the disclosed method, the formation of at least one additional layer is carried out after the annealing step. In still another embodiment, the additional layers comprise dielectric materials, semiconductor material, metals or any combination thereof.
In yet another embodiment of the disclosed method, the dielectric material is formed from an insulating material and selected from the list comprising insulating ribtan material, silicon dioxide (SiO2), silicon nitride (Si3N4), aluminum oxide (AI2O3), hafnium oxide
(HfO2), zirconium silicate, hafnium silicate, hafnium silicate oxynitride, titanium oxide, tantalum oxide, alumsilicate, carbon, carbon-doped silicon dioxide, and any combination thereof. The selection and combination of dielectric materials are known to those skilled in the art. In still another embodiment of the disclosed method, the conductor is selected from the list comprising copper, gold, silver, zinc, tin, indium, aluminum, titanium, doped poly- silicon, conductive ribtan layer as a semi-metal conductor, and any combination thereof. In one embodiment of the disclosed method, the substrate is made of one or several materials of the list comprising Si, Ge, SiGe, GaAs, diamond, quartz, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, metals, and any combination thereof. In another embodiment of the disclosed method, the substrate further comprises doped regions, circuit features, multilevel interconnects, and at least one patterned electrical-conducting ribtan layer.
In one embodiment of the disclosed method, the electrical-conducting ribtan layer possesses anisotropy of conductivity. In another embodiment, the electrical-conducting ribtan layer possesses an optical anisotropy. In still another embodiment, the graphene-like carbon-based structures are globally ordered on the substrate surface. The disclosed electrical-conducting ribtan layer has a global order or, in other words, such layer has globally ordered graphene-like carbon-based structures. Disclosed layer possesses the long- range order which is characterized by spatial correlation of graphene-like carbon-based structures within the limits of an entire layer. Spacing between the structures is approximately equal to 3.4±0.1 A in the direction approximately parallel to one of crystallographic axis over the entire substrate surface. Such spatial periodicity means that the electrical-conducting ribtan layer possesses the long-range coordination order. The disclosed layer may possess the long-range orientation order when hexagonal cells of graphene-like carbon-based structures are orientated substantially uniformly. The manufacturing process controls the direction of the crystallographic axes of the electrical- conducting layer over the entire substrate surface. Thus, the structure of the electrical- conducting layer differs from the structure of a polycrystalline layer, in which the uniform crystalline structure is formed within a separate crystal grain. The square of such a grain is much smaller than that of the substrate surface. The substrate surface has a limited influence on the crystal structure of the electrical-conducting layer, and consequently on the properties of electrical-conducting layer. The electrical-conducting layer may be formed on a part of the substrate surface, depending on the system design requirements. In another embodiment of the disclosed method, the electrical-conducting ribtan layer possesses semiconductor conductivity of n-type. In still another embodiment of the disclosed method, the electrical-conducting ribtan layer possesses semiconductor conductivity of p-type. In yet another embodiment of the disclosed method, the electrical-conducting ribtan layer possesses electrical conductivity approximating to metal-type conductivity. In one embodiment of the disclosed method, the graphene-like carbon-based structures have the form selected from the list comprising disk, plate, lamella, ribbon or any combination thereof. In another embodiment of the disclosed method, the distance between planes of the graphene-like carbon-based structures approximately equals to 3.4 ± 0.1 A.
In another embodiment of the disclosed method, said organic compound comprises at least one rylene fragment. Table 1 shows some examples of heterocyclic molecular systems comprising one or more rylene fragments of a general structural formula corresponding to structures 1-23.
In still another embodiment of the disclosed method, said organic compound comprises one or more anthrone fragment. Table 2 shows some examples of organic compounds comprising the anthrone fragments of a general structural formula corresponding to structures 24 - 31. Table 2. Examples of planar polycyclic molecular systems comprising anthrone fragments
In yet another embodiment of the disclosed method, the organic compound comprises planar fused polycyclic hydrocarbon. Table 3 shows some examples of the planar fused polycyclic hydrocarbons selected from the list comprising truxene, decacyclene, antanthrene, hexabenzotriphenylene, 1.2,3.4,5.6,7.8-tetra-(peri-naphthylene)- anthracene, dibenzoctacene, tetrabenzoheptacene, peropyrene, hexabenzocoronene, violanthrene, isoviolanthrene and of a general structural formula corresponding to structures 32-43.
Table 3. Examples of planar fused polycyclic hydrocarbons
In one embodiment of the disclosed method, the organic compound comprises one or more coronene fragment. Table 4 shows some examples of organic compounds comprising the coronene fragments of a general structural formula corresponding to structures 44-51.
Table 4. Examples of organic compounds comprising coronene fragments
In one embodiment of the disclosed method, at least one of the hetero-atomic groups A is selected from the list comprising imidazole group, benzimidazole group, amide group, substituted amide group, and hetero-atom selected from nitrogen, oxygen, and sulfur.
In another embodiment, at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in water or aqueous solution and is independently selected from the list comprising COO , SO3 , HPO3 , and PO32 and any combination thereof. In still another embodiment of the disclosed method, at least one of the substituents
S1, S2, S3 and S4 provides solubility of the organic compound in organic solvents and is independently selected from the list comprising CONR1R2, CONHCONH2, SO2NR1R2, R3, or any combination thereof, wherein R1, R2 and R3 are selected from hydrogen, an alkyl group, an aryl group, and any combination thereof, where the alkyl group has the general formula -(CH2)nCH3, where n is an integer from O to 27, and the aryl group is selected from the list comprising phenyl, benzyl and naphthyl.
In yet another embodiment of the disclosed method, at least one of the substituents Si, S2, S3 and S4 provides solubility of the organic compound in organic solvents and is selected from the list comprising (Ci-C3s)alkyl, (C2-C3s)alkenyl, and (C2-C35)alkinyl. In one embodiment, at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in organic solvents and comprises fragments selected from the list comprising structures 52-58 shown in Table 5, where R is selected from a list comprising linear or branched (Ci-C35) alkyl, (C2-C35)alkenyl, and (C2-C35)alkinyl.
Table 5. Examples of fragments of the substituents providing solubility
In another embodiment of the disclosed method, the organic compound is capable of forming rod-like supramolecules in the solution via π-π- interaction between the adjacent carbon-conjugated cores. In another embodiment, the disclosed method further comprises a step of the application of an external alignment action upon the applied solution in order to provide aligned orientation of the rod-like supramolecules. In another embodiment of the disclosed method, the application and alignment steps are carried out simultaneously. In still another embodiment of the disclosed method, the alignment step is carried out after the application step. In yet another embodiment, the rod- like supramolecules are aligned in the substrate plane.
In one embodiment of the disclosed method, at least one of the substituents Si, S2, S3 and S4 comprises molecular binding groups which number and arrangement provide for the formation of planar supramolecules from the organic compound molecules in the solution via non-covalent chemical bonds. In another embodiment of the disclosed method, at least one binding group is selected from the list comprising a hydrogen acceptor (AH), a hydrogen donor (DR), and a group having the general structural formula II
wherein the hydrogen acceptor (AH) and hydrogen donor (DH) are independently selected from the list comprising NH-group, and oxygen (O). In still another embodiment of the disclosed method, at least one of the binding groups is selected from the list comprising hetero-atoms, COOH, SO3H, H2PO3, NH, NH2, CO, OH, NHR, NR, COOMe, CONH2, CONHNH2, SO2NH2, -SO2-NH-SO2-NH2 and any combination thereof, where radical R is an alkyl group or an aryl group, the alkyl group having the general formula -(CH2)nCH3, where n is an integer from O to 27, and the aryl group being selected from the list comprising phenyl, benzyl and naphthyl.
In one embodiment of the method, at least one of the substituents S1, S2, S3 and S4 is selected from the list comprising -NO2, -Cl, -Br, -F, -CF3, -CN, -OCH3, -OC2H5, -OCOCH3, -OCN, -SCN, and -NHCOCH3.
In one embodiment of the disclosed method, the non-covalent chemical bonds are independently selected from the list comprising a single hydrogen bond, dipole-dipole interaction, cation - pi-interaction, Van-der-Waals interaction, coordination bond, ionic bond, ion-dipole interaction, multiple hydrogen bond, interaction via the hetero-atoms and any combination thereof. In another embodiment of the disclosed method, the planar supramolecule have the form selected from the list comprising disk, plate, lamella, ribbon or any combination thereof. In still another embodiment of the disclosed method, the planar supramolecules are predominantly oriented in the plane of the substrate. In one embodiment of the disclosed method, the drying and annealing steps are carried out simultaneously. In another embodiment, the drying and annealing steps are carried out sequentially.
In one embodiment of the disclosed method, the lithographic method is a photolithographic method, wherein the resist layer is a photoresist layer. In one embodiment, the formation of the photoresist layer comprises the following steps: treatment of the electrical-conducting ribtan layer in order to clean said electrical-conducting ribtan layer and increase adhesion of the photoresist layer to the electrical-conducting ribtan layer; coating of the photoresist layer by one or several methods selected from the list comprising spin coating, spray coating, flooding, and electrostatic method; and soft baking. In still another embodiment of the disclosed method, the photoresist is a positive photoresist. In yet another embodiment of the disclosed method, the photoresist is a negative photoresist. For positive resist, the exposed regions become more soluble and thus more easily removed in the development process. The final result is that the patterns formed in the positive resist are the same as those on a mask. For negative resists the exposed regions become less soluble, and the patterns formed in the negative resist are the reverse of the mask patterns. In one embodiment of the disclosed method, the formation of the pattern in the photoresist layer comprises the following steps: alignment of a mask with the electrical- conducting ribtan layer; exposure of the photoresist layer by means of light radiation through the mask; development of the photoresist layer; rinsing and drying of the electrical- conducting ribtan layer; and post-baking of the patterned photoresist layer. In another embodiment, the formation of the pattern in the photoresist layer further comprises a soft baking step after the step exposure of the photoresist layer by means of light radiation through the mask.
In one embodiment of the disclosed method, the exposure step is carried out by means of ultraviolet radiation, wherein a spectral range is defined by the photoresist used. In another embodiment of the disclosed method, the exposure step is carried out by means of a contact printing which is applied to the entire wafer, wherein the electrical-conducting ribtan layer is brought into the surface contact with the mask. In still another embodiment, the exposure step is carried out by means of proximity printing which is applied to the entire electrical-conducting ribtan layer, wherein there is a gap between the electrical-conducting ribtan layer and the mask. In yet another embodiment of the disclosed method, the exposure step is carried out by means of projection printing which is applied only to portions of the electrical-conducting ribtan layer, wherein there is a gap between the electrical-conducting ribtan layer and the mask.
In one embodiment of the disclosed method, the transfer step further comprises the following steps: etching of the electrical-conducting ribtan layer, wherein the layer is located underneath the patterned photoresist layer; and removing of the patterned photoresist layer. In another embodiment, the etching is by a wet etching method. In still another embodiment of the disclosed method, the etching is a dry-etching method selected from a list comprising plasma etching, reactive ion etching (RIE), sputter etching, magnetically enhanced RIE (MERIE), reactive ion beam etching, high-density plasma etching. In another embodiment, the mask is a phase-shifting mask.
In one embodiment of the disclosed method, the patterning lithographic method is an electron-beam projection lithographic method, wherein the resist layer is an electron resist layer. In another embodiment, the formation of the electron resist layer comprises the following steps: treatment of the electrical-conducting ribtan layer in order to clean the electrical-conducting ribtan layer and increase adhesion of the electron resist layer to the electrical-conducting ribtan layer; coating of the electron resist layer by one or several methods selected from the list comprising spin coating, spray coating, flooding, and electrostatic method, and drying of the electron resist layer. In another embodiment of the disclosed method, the electron resist is a positive electron resist. In still another embodiment of the disclosed method, the electron resist is a negative electron resist. For a positive electron resist made of polymer material, the polymer-electron interaction causes chemical bonds to be broken to form shorter molecular fragments. As a result, the molecular weight is reduced in the irradiated area, which can be dissolved subsequently in a developer solution that attacks the low-molecular-weight material. For a negative electron resist made of polymer material, the irradiation causes a radiation-induced polymer linking. The cross linking creates a complex three-dimensional structure with a molecular weight higher than that of the non-irradiated polymer. The non-irradiated electron resist can be dissolved in a developer solution that does not attack the high-molecular-weight material.
In one embodiment of the disclosed method, the formation of the pattern in the electron resist layer comprises the following steps: alignment of the mask with the electrical-conducting ribtan layer; exposure of the electron resist layer by means of electron- beam radiation through the mask; development of the electron resist layer; rinsing and drying of the electrical-conducting ribtan layer; and post-baking of the patterned electron resist layer. In another embodiment, the transfer step further comprises the following steps: etching of the electrical-conducting ribtan layer, wherein the layer is located underneath the patterned electron resist layer; and removing of the patterned electron resist layer. In still another embodiment of the disclosed method, the etching is a wet etching method. In yet another embodiment, the etching is a dry-etch method selected from a list comprising plasma etching, reactive ion etching (RIE), sputter etching, magnetically enhanced RIE (MERIE), reactive ion beam etching, and high-density plasma etching. In still another embodiment of the disclosed method, the mask is an electron scattering mask. In one embodiment of the disclosed method, the patterning lithographic method is an extreme-ultraviolet lithographic method, wherein the resist layer is a photoresist layer. In another embodiment, the spectral range of extreme-ultraviolet radiation is determined by the photoresist used. In still another embodiment of the disclosed method, the formation of the patterned photoresist layer further comprises a reflection mask. In yet another embodiment, the spectral range is approximately from 10 to 14 nanometers.
In one embodiment of the disclosed method, the lithographic method is an imprint photolithographic method, and the resist layer is an imprint resist layer. In another embodiment, the formation of the imprint layer comprises following steps:
- treatment of the electrical-conducting ribtan layer in order to clean the structure and increase adhesion of the imprint resist layer to the electrical-conducting ribtan layer;
- coating of the imprint resist layer by one or several methods selected from the list comprising spin coating, spray coating, flooding, and electrostatic method; and - drying of the imprint resist layer.
In still another embodiment of the disclosed method, the imprint resist is a thermal plastic material. In yet another embodiment, the formation of the pattern in the imprint resist layer comprises following steps:
- formation of a thickness contrast in the imprint resist layer, wherein a hard mould that contains features defined on its surface is used to emboss into imprint resist layer under controlled temperature and pressure conditions; and
- formation of a patterned resist layer, where the thickness contrast is transferred through the imprint resist layer via an anisotropic etching process.
In one embodiment of the disclosed method, the hard mould may be made of materials selected from the list comprising silicon, silicon dioxide, silicon carbide, silicon nitride, sapphire, and diamond. In another embodiment, the features have nano-scale sizes.
In a second preferred embodiment, the present invention provides a method of thermal patterning, comprising the following steps: application of a solution on a substrate, wherein the solution comprising at least one π-conjugated organic compound of a general structural formula I or any combination thereof:
where CC is a predominantly planar carbon-conjugated core; A is a hetero-atomic group; p is 0, 1, 2, 3, 4, 5, 6, 7, or 8; S1, S2, S3 and S4 are substituents; ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8; and sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8; drying with formation of a solid layer, and formation of a pattern in the solid layer by a local annealing, wherein the local annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of the hetero-atomic groups and the substituents from the solid layer and 2) fusion of the carbon-conjugated residues in order to form the predominantly planar graphene-like carbon-based structures.
In one embodiment of the disclosed method, the substrate is made of one or several materials of the list comprising Si, Ge, SiGe, GaAs, diamond, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, and metals, and any combination thereof. The substrate may further comprise doped regions, circuit features, multilevel interconnects, and at least one patterned ribtan layer. In still another embodiment of the disclosed method, the substrate is a heat-sensitive substrate.
In one embodiment of the disclosed method, the organic compound comprises one or more rylene fragments. Examples of the organic compounds 1 - 23 are given in Table 1.
In another embodiment of the disclosed method, the organic compound comprises one or more anthrone fragments. Examples of the organic compounds 24 - 31 are given in Table 2.
In still another embodiment of the disclosed method, the organic compound comprises planar fused polycyclic hydrocarbon. Examples of the hydrocarbons comprising truxene, decacyclene, antanthrene, hexabenzotriphenylene, 1.2,3.4,5.6,7.8-tetra-(peri- naphthylene)-anthracene, dibenzoctacene, tetrabenzoheptacene, peropyrene, hexabenzocoronene, violanthrene, isoviolanthrene (structures 32 - 43) are given in Table 3.
In yet another embodiment of the disclosed method, the organic compound comprises one or more coronene fragments. Examples of the organic compounds 44 - 51 are given in Table 4. In one embodiment of the disclosed method, at least one of the hetero-atomic groups A is selected from the list comprising imidazole group, benzimidazole group, amide group, substituted amide group, and hetero-atom selected from nitrogen, oxygen, and sulfur.
In another embodiment of the disclosed method, at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in water or aqueous solution and is selected from the list comprising COO , SO3 , HPO3 , and PO32 , and any combination thereof. In still another embodiment, at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in organic solvents and is selected from the list comprising CONR1R2, CONHCONH2, SO2NR1R2, R3, or any combination thereof, wherein R1, R2 and R3 are selected from hydrogen, an alkyl group, an aryl group, and any combination thereof, where the alkyl group has the general formula -(CH2)nCH3, where n is an integer from O to 27, and the aryl group is selected from the list comprising phenyl, benzyl and naphthyl. In yet another embodiment of the disclosed method, at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in organic solvents and is selected from the list comprising (Ci-C3s)alkyl, (C2-C3s)alkenyl, and (C2- C35)alkinyl. In one embodiment, at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in organic solvents and comprises fragments selected from the list comprising structures 52-58 shown in Table 5, where R is selected from a list comprising linear or branched (C1-C35) alkyl, (C2-C35)alkenyl, and (C2-C35)alkinyl. In another embodiment of the disclosed method, the organic compound is capable of forming rod-like supramolecules in the solution via π-π- interaction between the adjacent carbon-conjugated cores. The disclosed method further comprises a step of the application of an external alignment action upon the applied solution in order to provide aligned orientation of the rod-like supramolecules. In another embodiment, the application and alignment steps are carried out simultaneously. In still another embodiment of the disclosed method, the alignment step is carried out after the application step. In yet another embodiment of the disclosed method, the rod-like supramolecules are aligned in the substrate plane.
In one embodiment of the disclosed method, at least one of said substituents S1, S2, S3 and S4 comprises at least one molecular binding group which number and arrangement provide for the formation of planar supramolecules from the organic compound molecules in the solution via non-covalent chemical bonds. In another embodiment, at least one binding group is selected from the list comprising a hydrogen acceptor (AH), a hydrogen donor (DR), and a group having a general structural formula II
wherein the hydrogen acceptor (AR) and hydrogen donor (DR) are independently selected from the list comprising NH-group, and oxygen (O). In still another embodiment of the disclosed method, at least one of the binding groups is selected from the list comprising hetero-atoms, COOH, SO3H, H2PO3, NH, NH2, CO, OH, NHR, NR, COOMe, CONH2, CONHNH2, SO2NH2, -SO2-NH-SO2-NH2 and any combination thereof, where radical R is an alkyl group or an aryl group, the alkyl group having the general formula -(CH2)nCH3, where n is an integer from O to 27, and the aryl group being selected from the list comprising phenyl, benzyl and naphthyl.
In one embodiment of the method, at least one of substituents S1, S2, S3 and S4 is selected from the list comprising -NO2, -Cl, -Br, -F, -CF3, -CN, -OCH3, -OC2H5, -OCOCH3, -OCN, -SCN, and -NHCOCH3.
In one embodiment of the disclosed method, the non-covalent chemical bonds are independently selected from the list comprising a single hydrogen bond, dipole-dipole interaction, cation - pi-interaction, Van-der-Waals interaction, coordination bond, ionic bond, ion-dipole interaction, multiple hydrogen bond, interaction via the hetero-atoms, and any combination thereof. In another embodiment, the planar supramolecule have the form selected from the list comprising disk, plate, lamella, ribbon and any combination thereof. In still another embodiment of the disclosed method, the planar supramolecules are predominantly oriented in the plane of the substrate. In one embodiment of the disclosed method, the local annealing is carried out by the laser thermal patterning process using one or several lasers. In another embodiment, the local annealing is carried out by a radiation selected from the list comprising electromagnetic radiation, X-ray, UV-radiation, infrared radiation, and any combination thereof. In still another embodiment of the disclosed method, the local annealing is carried out with a direct write technique. In yet another embodiment of the disclosed method, the local annealing is carried out using a pattern transfer mask-based technique. In another embodiment, the local annealing is carried out by a heating element located in close proximity with the surface of the solid layer. In another embodiment, the heating element is a hard mould that contains features defined on its surface. In yet another embodiment, the features have nano-scale sizes.
In still another embodiment of the disclosed method, the local annealing comprises the following sequence of steps:
- forming a patterned thermal-resist layer on the solid layer via one of lithographic methods;
- exposing the thermal-resist layer to infrared radiation; and
- removing of the thermal-resist layer with one of the etch methods. In yet another embodiment of the disclosed method, the local annealing comprises the sequence of following steps:
- depositing of the metal lines on the surface of the solid layer; and
- heating of the metal lines and the surface by passing the electric current through the metal lines. In one embodiment of the disclosed method, the local annealing is carried out using a focused ultrasound beam and direct write technique.
In another embodiment of the disclosed method, the local annealing comprises the following sequence of steps:
- forming of a patterned resist layer on the solid layer via one of lithographic methods;
- executing an exothermic chemical reaction on a surface of the solid layer; and
- removing of the resist layer with one of the etch method.
The pattern to be transferred onto a multilayer structure may be formed on the surface of the multilayer structure using a positive resist. An exothermic chemical reaction is created on the exposed areas of the pattern by introducing the chemicals known to one skilled in the art. This reaction creates local heating, which causes local annealing of the ribtan material. In still another embodiment of the disclosed method, the local annealing is carried out by applying local pressure to the surface of the solid layer. The pattern to be transferred onto a multilayer structure is formed on one surface of a block of material forming a hard mould that contains features defined on its surface. The hard mould is applied to the surface of the multilayer structure with sufficient force to create local heating and deformation of the crystal structure, transferring the pattern into the ribtan layer. In yet another embodiment of the disclosed method, the features may have nano-scale sizes.
In one embodiment of the disclosed method, the local annealing is carried out by passing a current through at least one portion of the solid layer. In another embodiment, the passing of the current is carried out using the scanning tunneling microscope (STM) tip, array of STM tips, electron beam, array of electron beams, and any combination thereof. In one embodiment of the disclosed method, the local annealing is carried out by a DC, AC or pulsed electric current flowing between a hard mould, which comprises features defined on its surface and is brought into contact with the surface of the multilayer structure or into close proximity with the surface, and an electrode located on opposite surface of the multilayer structure. In another embodiment, the features have nano-scale sizes. Electricity is passed through the hard mould and the multilayer structure to the electrode, creating local heating and annealing the ribtan material.
In a third preferred embodiment, the present invention provides a method of direct lithographic patterning, comprising the sequence of following steps: depositing a wet pattern on a substrate using a solution which comprises at least one π-conjugated organic compound of the general structural formula I or any combination thereof:
where CC is a predominantly planar carbon-conjugated core; A is a hetero-atomic group; p is 0, 1, 2, 3, 4, 5, 6, 7, or 8; S1, S2, S3 and S4 are substituents; ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8; and sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8; drying of the wet pattern with the formation of a solid pattern, and annealing with the formation of a solid pattern comprising graphene-like carbon-based structures and possessing electrical- conductivity, wherein said annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of hetero-atomic groups and substituents from the solid pattern and 2) fusion of the carbon-conjugated residues in order to form the predominantly planar graphene-like carbon-based structures.
The method of direct lithographic patterning refers to methods in which patterns of materials are supplied to (and sometimes removed from) a substrate simply by physical contact or exposure through the mediating use of stamps, nozzles (e.g., inkjet printheads), or masks (e.g., silk screens). In this method the depositing step may be carried out by at least one of the techniques selected from the list comprising a printing, a reverse-imprinting, an ink-jet printing, a drawing by a ruling pen (drawing-pen), a dip-pen lithographic technique, and any combination thereof. Direct printing methods can be used in an integrated circuit, from the metal contacts to the insulating elements to the active transport layers. Direct printing methods may be either parallel or serial in their operation, depending upon how the pattern is defined. Pattern definition may come, for example, from relief features on a stamp, from masks that protect regions on a substrate from exposure to a printed material, or by focused jets that trace a path across the substrate. These methods of direct lithographic patterning show promise for large-area, low-cost implementation mostly due to the simplicity inherent to printing processes (minimization or absence of resists, solvents, and tooling).
The method of direct lithographic patterning which uses stamps may be successfully applied to many different areas of organic electronics. Their ability to pattern large areas in a single process step (i.e., their parallel operation) and their high resolution represent key features of these approaches. Generally, a stamp supplies a solution which comprises at least one π-conjugated organic compound of the general structural formula I to a substrate by physical contact. This transferred material acts as a functional layer of an organic device or an integrated circuit. The "stamps" used for this process come in widely different forms and can be made of materials ranging from rigid solids such as glass or silicon to flexible plastic sheets to soft, viscoelastic elastomers, most notably polydimethylsiloxane (PDMS). For large-area application, these stamps should be thin to enable bending that can facilitate their removal from rigid, nonflexible device substrates, such as thick glass or semiconductor wafers. Resolution limits are often very good, limited by the resolution of the stamps themselves or the materials characteristics of the solutions. In many instances, method of direct lithographic patterning reduces the number of process steps by minimizing the use of sacrificial layers or even eliminating them by employing purely additive approaches. In addition, many of the methods are noninvasive, thermally and chemically, leading to simplicity in process engineering.
In one embodiment of the present method of direct lithographic patterning, the depositing step further comprises preliminary microcontact printing of chemicals which may serve as templates for patterning solution comprising at least one π-conjugated organic compound of the general structural formula I by serving as wetting or de-wetting patterns. A wide variety of printable materials can be employed for these approaches. In one embodiment of this method, hydrophobic siloxane oligomers present in common PDMS elastomer transfer onto the contacted substrates. Those oligomer films can function as dewetting templates for patterning solution comprising at least one π-conjugated organic compound of the general structural formula I with resolution as good as 1 μm. The solution moistens the unstamped, hydrophilic surfaces but leaves the printed, hydrophobic surfaces dry. This disclosed method may be used to make organic thin film transistors (OTFTs) on flexible plastic substrates. In another embodiment, microcontact printed templates may also be used as wetting patterns in which solutions comprising at least one π-conjugated organic compound of the general structural formula I are deposited on the printed regions and not on the bare regions, in contrast to the aforementioned embodiment.
In a set of the disclosed methods that we refer to as "method of direct lithographic patterning", the materials printed from a stamp are the actual functional materials for organic electronics, integrated circuits or other applications. The advantages of this approach include, in many cases, the ability to pattern several types of solution comprising at least one π-conjugated organic compound of the general structural formula I on a single device substrate without exposing it to solvents or other invasive processing and high levels of resolution. The requirements for these methods are: a stamp that can support the solutions and may be contacted to a substrate, and a mechanism for the transfer of this solution from the stamp to the substrate. These substrates can use special surface chemistries, conformable adhesive layers, or other means to guide preferential adhesion. The adhesive layer may be made of polyvinylbutyral or polyacrylate. Stamps suitable for transfer printing may comprise soft elastomers, such as PDMS, and also hard backings, especially when pressure is applied to guide the transfer and/or when the substrate has a soft, conformable surface to facilitate contact. The features of relief on the stamps usually define the patterns in the transfer printed materials. Solutions comprising at least one π- conjugated organic compound of the general structural formula I that are transfer-printed can form a variety of layers of organic electronic systems or integrated circuits, from conductors to semiconductors to dielectrics.
In one embodiment of the disclosed method, two parts of an organic device or integrated circuit may be fabricated separately whereupon these parts incorporate with each other. The disclosed method is the stamp-based printing method for which two parts are joined for the fabrication and patterning of the materials. Each part of the device can be formed by the disclosed method of direct lithographic patterning. The disclosed method is similar to the well-known lamination technology - however in case of lamination the devices are formed by the incorporation of two parts but no material is transferred. In one embodiment of the disclosed method, the substrate is made of one or several materials of the list comprising Si, Ge, SiGe, GaAs, diamond, quartz, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, metals and any combination thereof. In another embodiment of the disclosed method, the substrate further comprises doped regions, circuit features, multilevel interconnects, and at least one patterned ribtan layer.
In one embodiment of the disclosed method, the organic compound comprises one or more rylene fragments. Examples of the organic compounds 1 - 23 are given in Table 1.
In another embodiment of the disclosed method, the organic compound comprises one or more anthrone fragments. Examples of the organic compounds 24 - 31 are given in Table 2.
In still another embodiment of the disclosed method, the organic compound comprises planar fused poly cyclic hydrocarbons. Examples of the hydrocarbons comprising truxene, decacyclene, antanthrene, hexabenzotriphenylene, 1.2,3.4,5.6,7.8-tetra-(peri- naphthylene)-anthracene, dibenzoctacene, tetrabenzoheptacene, peropyrene, hexabenzocoronene, violanthrene, isoviolanthrene (structures 32 - 43) are given in Table 3.
In yet another embodiment of the disclosed method, the organic compound comprises one or more coronene fragments. Examples of the organic compounds 44 - 51 are given in Table 4. In one embodiment of the disclosed method, at least one of the hetero-atomic groups
A is selected from the list comprising imidazole group, benzimidazole group, amide group, substituted amide group, and hetero-atom selected from nitrogen, oxygen, and sulfur. In another embodiment of the disclosed method, at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in water or aqueous solution and is selected from the list comprising COO , SO3 , HPO3 , and PO32 and any combination thereof. In still another embodiment of the disclosed method, at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in organic solvents and is selected from the list comprising CONR1R2, CONHCONH2, SO2NR1R2, R3, or any combination thereof, wherein R1, R2 and R3 are selected from hydrogen, an alkyl group, an aryl group, and any combination thereof, where the alkyl group has the general formula - (CH2)nCH3, where n is an integer from O to 27, and the aryl group is selected from the list comprising phenyl, benzyl and naphthyl. In yet another embodiment of the disclosed method, at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in organic solvents and is selected from the list comprising (Ci-C35)alkyl, (C2- C35)alkenyl, and (C2-C35)alkinyl. In one embodiment of the disclosed method, at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in organic solvents and comprises fragments selected from the list comprising structures 52-58 shown in Table 5, where R is selected from a group comprising linear or branched (C1-C35) alkyl, (C2-C35)alkenyl, and (C2-C35)alkinyl.
In another embodiment of the disclosed method, the organic compound is capable of forming rod-like supramolecules in the solution via π-π- interaction between the adjacent carbon-conjugated cores. In another embodiment of present invention, the disclosed method further comprises a step of the application of an external alignment action upon the applied solution in order to provide an aligned orientation of the rod-like supramolecules. In another embodiment of the disclosed method, the application and alignment steps are carried out simultaneously. In still another embodiment of the disclosed method, the alignment step is carried out after the application step. In yet another embodiment of the disclosed method, the rod-like supramolecules are aligned in the substrate plane.
In one embodiment of the disclosed method, the at least one of the substituents S1, S2, S3 and S4 comprises molecular binding groups which number and arrangement provide for the formation of planar supramolecules from the organic compound molecules in the solution via non-covalent chemical bonds. In another embodiment of the disclosed method, at least one binding group is selected from the list comprising a hydrogen acceptor (AR), a hydrogen donor (DR), and a group having a general structural formula II
wherein the hydrogen acceptor (AR) and hydrogen donor (DR) are independently selected from the list comprising NH-group, and oxygen (O). In still another embodiment, at least one of the binding groups is selected from the list comprising hetero-atoms, COOH, SO3H, H2PO3, NH, NH2, CO, OH, NHR, NR, COOMe, CONH2, CONHNH2, SO2NH2, -SO2-NH- SO2-NH2 and any combination thereof, where radical R is an alkyl group or an aryl group, the alkyl group having the general formula -(CH2)nCH3, where n is an integer from O to 27, and the aryl group being selected from the list comprising phenyl, benzyl and naphthyl.
In one embodiment of the method, at least one of the substituents S1, S2, S3 and S4 is selected from the list comprising -NO2, -Cl, -Br, -F, -CF3, -CN, -OCH3, -OC2H5, -OCOCH3, -OCN, -SCN, and -NHCOCH3. In one embodiment of the disclosed method, the non-covalent chemical bonds are independently selected from the list comprising a single hydrogen bond, dipole-dipole interaction, cation - pi-interaction, Van-der-Waals interaction, coordination bond, ionic bond, ion-dipole interaction, multiple hydrogen bond, interaction via the hetero-atoms and any combination thereof. In another embodiment, the planar supramolecules have the form selected from the list comprising disk, plate, lamella, ribbon or any combination thereof. In still another embodiment of the disclosed method, the planar supramolecules are predominantly oriented in the plane of the substrate.
In one embodiment of the disclosed method, the solution is an isotropic solution. In another embodiment of the disclosed method, said solution is a lyotropic liquid crystal solution. In still another embodiment, the disclosed method further comprises an alignment action, wherein the alignment action is simultaneous with application of the wet pattern on the substrate. In yet another embodiment of the disclosed method, the deposition step is carried out by at least one of techniques selected from the list comprising a printing, a reverse-imprinting, an ink-jet printing, a drawing by a ruling pen (drawing-pen), a dip-pen lithographic technique, and any combination thereof. In one embodiment of the disclosed method, the drying and annealing steps are carried out simultaneously. In another embodiment of the disclosed method, the drying and annealing steps are carried out sequentially.
One embodiment of the disclosed method is named thermal-imprint lithography, and for this method the step of deposition of a wet pattern on a substrate comprises
- application of the solution on a substrate, wherein the solution comprises at least one π-conjugated organic compound of the general structural formula I and formation of a wet layer on the substrate; and
- embossing of a hard mould into the wet layer, wherein the hard mould contains features defined on its surface and formation of a thickness contrast in the wet layer.
In another embodiment of the disclosed method, the features have nano-scale sizes. In yet another embodiment of the disclosed method, the drying of the wet layer is carried out during pressing the hard mould into the wet layer, and a solid layer with the thickness contrast is formed. In another embodiment of the present invention, the disclosed method further comprises a step of transferring thickness contrast through the solid layer via an anisotropic etching process, wherein this step is carried out after the drying step.
In a fourth preferred embodiment, the present invention provides an integrated circuit, comprising a ribtan layer on the substrate, wherein the ribtan layer is patterned to define at least one functional structure, wherein the method of patterning is any of the methods of patterning disclosed in the present invention.
In one embodiment of the disclosed integrated circuit, the substrate is made of one or several materials of the list comprising Si, Ge, SiGe, GaAs, diamond, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, metals and any combination thereof. In another embodiment, the substrate further comprises doped regions, circuit features, multilevel interconnects, and at least one patterned ribtan layer. In still another embodiment of the disclosed integrated circuit, the substrate comprises an insulator.
In one embodiment of the disclosed integrated circuit, the ribtan layer has a graphene- like structure of nano-scale thickness. In another embodiment, the ribtan comprises at least one graphene-like strip. In still another embodiment, the ribtan layer comprises at least one graphene-like carbon-based strip. In one embodiment of the disclosed integrated circuit, the ribtan layer is patterned to form at least one electronic device. In another embodiment, the electronic device comprises a transistor. In still another embodiment of the disclosed integrated circuit, the transistor comprises a source electrode; a drain electrode, spaced apart from the source electrode; a connector being in electrical communication with both the source electrode and the drain electrode; and a gate electrode spaced apart from the connector at a distance such that an electron transport property of the connector changes when bias voltage is applied to the gate electrode so as to induce a field that interacts with the connector, and wherein the connector is made by patterning of ribtan layer. In yet another embodiment, at least one electrode selected from the list comprising a source electrode, a drain electrode and a gate electrode comprises the ribtan layer. In one embodiment, the electronic device comprises at least one logic gate. In another embodiment of the disclosed integrated circuit, the electronic device comprises at least one logic directional coupler.
In still another embodiment, the electronic device comprises at least one interferometer. In yet another embodiment, the interferometer comprises a source electrode; a drain electrode; a loop-like structure, having a first branch and a spaced-apart second branch being in electrical communication with the source electrode and with the drain electrode; at least one gate electrode disposed adjacent to the first branch, that is capable of exerting an electrical field substantially only on the first branch; and a sensor that may sense interference between electrons passing through the first branch and electrons passing through the second branch, and wherein the loop-like structure is made by patterning of ribtan layer. In another embodiment of the disclosed integrated circuit, at least one electrode selected from the list comprising a source electrode, a drain electrode and a gate electrode comprises the ribtan layer. In still another embodiment of the disclosed integrated circuit the interferometer comprises a Mach-Zender device.
The present invention will now be described more fully hereinafter with reference to the following examples, in which preferred embodiments of the present invention are shown. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the thickness of layers and regions are exaggerated for clarity. EXAMPLES
Example 1
Example 1 describes a formation of one embodiment of the electrical-conducting ribtan layer. The ribtan layer comprising graphene-like carbon-based structures was formed by a mixture of bis(carboxybenzimidazoles) of prerylenetetracarboxylic acids (bis-carboxy DBI PTCA), which predominantly planar carbon-conjugated cores are shown in Table 1, ## 4 and 5. As a first step, a water solution of bis-carboxy DBI PTCA was applied on a substrate. The solution comprised a mixture of six isomers as shown in Figure 1. Bis- carboxy DBI PTCA is a π-conjugated organic compound, where the predominantly planar carbon-conjugated core (CC as in formula I) comprises rylene fragments, the benzimidazole groups serve as hetero-atomic groups and carboxylic groups serve as substituents providing solubility. The molecular structure provides for the formation of rod-like supramolecules. Quartz was used as a substrate material as an example only. The Mayer rod technique was used to coat the water-based solution of bis -carboxy DBI PTCA. During the second step the drying was performed at 40 degrees C and humidity of approximately 70%. By the end of the drying step, the layer usually retained about 10% of the solvent. As a result of the coating and drying steps the ribtan layer comprises rod-like supramolecules oriented along the coating direction. Figure 3 schematically shows the supramolecule 1 oriented along the y-axis and located on the substrate 2. The distance between planes of bis-carboxy DBI PTCA is approximately equal to 3.4 A.
The annealing step was carried out in vacuum or inert gas. It included two stages: 1) exposure of bis-carboxy DBI PTCA layer at 350 0C for 30 minutes to carry out a partial pyro lysis of the organic compound with at least partial removal of the hetero-atomic groups and the substituents from the layer, and 2) fusion of the carbon-conjugated residues in the temperature range of 650 - 900 0C for 10 - 300 minutes in order to form the predominantly planar graphene-like carbon-based structures. The annealing regime is shown in Figure 4. At least part of the substituents S1, S2, S3 and S4 and hetero-atomic groups have been removed from the solid layer. Thickness of the bis-carboxy DBIPTCA layer after the drying stage was about 50 nm. After the annealing, thickness of the layer was decreased to about 70 % of the initial thickness. This value was essentially reproducible in the above referenced time and temperature ranges. A thermo gravimetric analysis of the layer of bis-carboxy DBI PTCA is shown in Figure 5. The formation of the layer of bis-carboxy DBI PTCA had three main stages: 1) water and ammonia removal from the solid precursor layer (24-2500C), 2) decarboxylation process (353-415°C), and 3) DBI PTCA layer partial pyrolysis with carbon-conjugated residues forming (541-717°C). Formula weight (FW) of Bis(carboxybenzimidazoles) of PTCA is shown in Table 6.
Table 6. Formula weight (FW) of Bis(carboxybenzimidazoles) of PTCA
The resulting carbon-conjugated residues form the intermediate anisotropic structure as shown in Figure 6.
Further annealing results in the formation of predominantly planar graphene-like carbon-based structures via thermal polymerization of the carbon-conjugated residues. One possible graphene-like carbon-based structure is shown schematically in Figure 7. The graphene-like structure comprises a substantially planar hexagonal carbon core (the carbon atoms are marked as black circles in Figure 7). The hexagonal carbon core possesses high electrical conductivity which is close to the conductivity of metal. Atoms of hydrogen (white circles in Figure 7) are positioned along the perimeter of graphene-like carbon-based structure. Figure 8 schematically shows the anisotropic ribtan layer 3 on the substrate 2 after the annealing step.
TEM image of the metallic ribtan layer formed on a substrate is shown in Figure 9.
There is global preferential orientation in the layer order. The orientation was also shown by electron diffraction images (Figure 10). The diffraction image shows that the ribtan layer has a layered structure similar to α-graphite. There are two clear maxima related to
002 and 002 diffraction reflexes that correspond to ID ordering in the layer in the direction perpendicular to graphene planes. The interplanar space is about 3.4 A. Absorption spectra in polarized light of the annealed and dried layer of bis-carboxy DBI PTCA are shown in Figure 11. The absorption spectra of the initial samples and samples after formation of the metallic ribtan layer step (c) show an optical anisotropy.
Figure 12 shows Raman spectrum of the annealed samples. The spectrum includes typical lines for sp2 bonded carbon material. The position of these line G) and its FWHM suggests that the metallic ribtan layer consists of a graphene-like layered structure. Lines D and 2D are split which means that the surface of ribtan layers consist of edges of graphene- like layers. Detection of Raman spectra in different points of the sample proves homogeneity of phase composition and distribution of structural defects over ribtan surface (Figure 13).
Measurements of resistivity of the metallic ribtan layers have been made using a standard 4-point probe technique. The resistivity of the metallic ribtan layers was measured for parallel (par) and perpendicular (per) to coating direction in order to detect electrical anisotropy of the ribtan layers. Results of the measurements are shown in Figures 14 and
15.
There is some anisotropy of resistivity along graphene-like nanoribbons (per) which is lower than resistivity across the nanoribbons (par). The resistivity strongly depends on fusion temperature and exposure time. Figure 14 shows resistivity as a function of maximum annealing temperature (Tmax) and Figure 15 shows resistivity as a function of time of a sample exposure at maximum temperature.
Generally, resistivity decreases with increasing of time and temperature of fusion. The resistivity perpendicular to the coating direction is about two - three times smaller than resistivity parallel to the coating direction. Thus, the ribtan layer possesses anisotropy of resistivity. Such anisotropy of the resistivity corresponds to a better charge transport in the direction along the graphene-like carbon-based structures.
The voltage-current characteristics obtained at different annealing temperatures on bis-carboxy DBIPTCA layer are shown in Figure 16. The ribtan layers are characterized by dependence of conductivity (a reciprocal value of electrical resistivity) on annealing temperature and by transition: dielectric -semiconductor -conductor state. The high value of the measured conductivity proves the global (continuous) character of the ribtan layer.
Example 2 This example describes the formation of another the electrical-conducting ribtan layer. The ribtan layer was formed on a substrate on the basis of a mixture of 2-oxo-2,3- dihydro-l"H-l,2':r,2"-terbenzimidazoletricarboxylic acids and 2-oxo-2,3-dihydro-l'H-l,2'- bibenzimidazole-dicarboxylic acids. The compounds correspond to the structures 60 and 61 of Table 6 and are shown in Figure 2. 15g of a mixture of 2-oxo-2,3-dihydro-l"H-l,2':r,2"- terbenzimidazole-tricarboxylic acids and 2-oxo-2,3-dihydro-l'H-l,2'- bibenzimidazoledicarboxylic acids were dissolved in 85g of dimethylformamide and stirred at 200C until total dissolution of the solid phase. Then the resulting solution was filtered. Quartz plates were prepared for coating by treating in a 10% NaOH solution for 30 min, rinsing with deionized water, and drying in airflow with the aid of a compressor. Prior to the coating, samples were rinsed with isopropyl alcohol. The obtained solution was applied onto a quartz plate with a Mayer rod #4 at a temperature of approximately 23°C and relative humidity of about 50%. The layer was dried in a hot air flow. The dried samples were heated to 2500C for 30 minutes.
The annealing step was carried out in vacuum at 65O0C for approximately 20 minutes. The layer thickness dropped from approximately 100 nm to 60 nm. The duration and temperature of this step were selected so as to ensure partial pyrolysis of the organic compound with formation of carbon-conjugated residues. The substituents and the hetero- atomic groups have been at least partially removed from the solid layer. The further annealing resulted in the formation of predominantly planar graphene-like carbon-based structures via thermal polymerization of the carbon-conjugated residues.
One possible embodiment of such graphene-like carbon-based structures is shown schematically in Figure 7. The graphene-like structure comprises substantially planar hexagonal carbon core (the carbon atoms are marked as black circles in Figure 7). The hexagonal carbon core possesses high electric conductivity which approaches the conductivity of metals. The annealing step was carried out in a hydrogen flow and the atoms of hydrogen (white circles in Figure 7) were positioned along the perimeter of graphene-like carbon-based structure. Figure 16 shows schematically the anisotropic ribtan layer (3) on the substrate (2) after the annealing step, where the carbon-based structures have a homeotropic alignment.
Example 3 The example demonstrates a method of photolithographic patterning of ribtan layer.
The ribtan layer was formed as described in Example 1 or Example 2. Figures 18-22 illustrate this embodiment of the present invention during various patterning steps. The first step of patterning was formation of a HPR (positive) photoresist layer on the ribtan surface. The ribtan layer on a substrate was placed in a clean room which was illuminated with yellow light, since photoresist is not sensitive to wavelengths higher than approximately 0.5 μm. The ribtan sample was held on a vacuum spindle, and a liquid resist was applied to the center of the sample. The structure was then rapidly accelerated up to a constant rotational speed 3000 rpm, which was maintained for 40 second. Figure 18 schematically shows ribtan layer (3) on a substrate (2) coated by photoresist layer (4). As known to the person skilled in the art, many variations may be used as methods of coating of samples with the photoresist layer, such as spray coating, flooding, electrostatic method, and any other methods known in the art.
After the spinning step, the multilayer structure was exposed to a soft bake (at 100 0C for 60 seconds) in order to remove the solvent from the photoresist layer and to increase adhesion of the photoresist to the ribtan layer.
The sample coated by photoresist layer was aligned with respect to the photomask in an optical lithographic system. The photomask has a pattern corresponding to a desired functional structure, and the photoresist was exposed to UV light through the mask during 120 seconds, as shown in Figure 19. Figure 19 schematically shows the multilayer structure comprising the substrate (2), the metallic ribtan layer (3), and the photoresist layer (4), and the mask (5). The mask (5) includes first translucent or transparent regions (6), and second opaque regions (7). The exposed photoresist relaxed in air at room temperature during about 1 minute. Then photoresist was dissolved in the mixture of HPR developer with DI water (1 :3) during 70 seconds. The developed structure was then rinsed the flow of DI water during about 3 minutes and dried in nitrogen flow.
Figure 20 shows the produced structure comprising the ribtan layer (3) and the patterned photoresist layer (8). The structure shown in Figure 20 was then put in oxygen plasma that provides etching of the ribtan layer (3). Figure 21 shows the patterned ribtan layer (9) with a patterned photoresist layer (8). Then, the photoresist was dissolved in acetone, leaving in the ribtan layer (9) the pattern that was the same as the opaque regions (7) on the mask shown in Figure 19.
Finally, the patterned ribtan layer (9) has been formed on the substrate (2), as shown in Figure 22.
Example 4
Example 4 describes a method of electron-beam projection lithographic patterning of ribtan layer. Figures 23-27 illustrate this embodiment of the present invention with illustration of the various patterning steps. The ribtan layer on a substrate was formed as described in Example 1 or Example 2, and as shown.
The ribtan layer on a substrate was held on a vacuum spindle, and a polymer electron resist was applied to the center of the multilayer structure. The structure was then rapidly accelerated up to a constant rotational speed, which was maintained for about 40 seconds. The spin speed was generally in the range of 1000 - 10000 rpm to coat a uniform electron resist layer 10 up to about 0.5 to 1 μm thick, as shown in Figure 23. The positive electron resist was used that comprises poly-methyl methacrylate and poly-butene-1 sulfone. The positive electron resist allows achievement of resolution of approximately 0.1 μm. After the spinning step, the multilayer structure was exposed to a soft bake (typically at approximately 90° - 12O0C for about 60 to 120 second) in order to increase an electron resist adhesion to the multilayer structure.
In this case the SCALPEL (Scattering with angular limitation projection electron- beam lithography) system was used. Figure 24 schematically shows the SCALPEL-system which uses a scattering mask 11 to conduct the reduction projection lithography with a scanner. The mask was uniformly illuminated by a parallel electron beam of approximately lOOkeV 12. The scattering mask was comprised of a thin (100 - 150 nm), low-atomic- number layer 13, and a thin (30 - 60 nm), high-atomic-number patterned layer 14. Although the scattering mask 11 was almost completely electron transparent at the energies used, contrast was generated by utilizing the difference in electron-scattering characteristics between the layer 13 and the patterned layer 14. The layer 13 of low-atomic- number material scatters electrons weakly with small angles, whereas the patterned layer 14 of high-atomic-number scatters most electrons strongly with high angles. A SCALPEL aperture 15 in the back- focal plane of the projection optics 16 blocks the strongly scattered electrons, forming a high-contrast pattern 17 on the electron resist layer 10.
The exposed electron resist was dissolved in the developer. The electron resist development was performed by flooding the exposed structure with the developer solution. The developed structure was then rinsed and dried. Figure 25 shows the resulting structure comprising the ribtan layer on a substrate and the patterned electron resist layer 18. The structure shown in Figure 25 was then put in oxygen plasma that provides etching of the ribtan layer 3. Figure 26 shows the patterned ribtan layer (9) with patterned electron resist layer (18). Then the patterned electron resist layer 18 was removed. At last, the patterned ribtan layer 19 has been formed on the substrate 2, as shown in Figure 27.
Example 5
Example 5 describes a method of extreme-ultraviolet lithographic patterning of ribtan layer. Figure 28 illustrates this embodiment of the present invention. The multilayer structure comprising a substrate 2 and a ribtan layer 3, and a photoresist layer 4 was formed as described in Example 1 or Example 2, resulting in the structure as shown in Figure 18.
In the Example 5 an extreme-ultraviolet (EUV) lithography system was used. Figure 28 shows a schematic diagram of EUV lithographic system, comprising a source of extreme-ultraviolet radiation 20, a reflection mask 21, and a 4><reduction camera 22. A laser-produced plasma was used as the EUV source of λ = 10 - 14 nm EUV light. The EUV radiation was reflected by the reflection mask 21 that was produced by patterning an absorber material deposited on the multilayer structure coated on the flat silicon plate. The EUV radiation was reflected from the non-patterned regions of the reflected mask 21, passed through the 4><reduction camera 22, and transferred the pattern into the photoresist layer 4 on the multilayer structure. The subsequent steps of formation of a pattern in the ribtan layer were carried out as described by the Example 3.
Example 6 The example describes a method of transferring a pattern on a ribtan layer via imprint lithography. The multilayer structure comprising a substrate 2 and a ribtan layer 3 was formed as described in Example 1 or Example 2. Then the layer 23 made of an imprint resist was formed on the multilayer structure, as shown in Figure 29. Thermal plastic materials were used as the imprint resists, and a suitable imprint temperature was chosen between about 700C to 800C above the material's glass transition temperature (Tg). This choice is explained by considering the typical deformation behavior of a thermal plastic polymer as a function of the temperature. At a temperature below Tg, the major contribution to the deformation comes from the elongation of the atomic distance, and the deformation is ideal elastic. The Young's modulus for glassy polymers just below Tg is approximately constant over a wide range of polymers (3 x 109 Pa), and the magnitude of deformation is very small. Above Tg, local motion of chain segments takes place and the modulus of the material drops by several orders of magnitude. However, the entire chains are still fixed by the temporary network of entanglements. A rubber-elastic plateau region exists beyond Tg, where a relatively large deformation may occur due to extension of chain segments fixed between entanglement points. The modulus stays relatively constant in the rubbery state, and the deformation will recover after the force is released. Next is the rubbery flow region for linear amorphous polymers, but it does not occur for cross-linked polymers. Finally, with a further increase in temperature, the viscous liquid flow state is reached. In this regime motion of entire chains takes place and the polymer flows by chain sliding. The modulus and viscosity are further reduced in this region and the deformation is irreversible, which makes it the right temperature range for imprint lithographic patterning. It was perceived that a good imprinting result can be acquired when the imprinting temperature was set to be higher than the flow temperature (Tf) of the polymer. Empirically an optimal imprinting temperature was found about 70 to 800C above the Tg of the material used. A poly(benzyl methacrylate) (Tg = 54°C) was used as the imprint resist. A hard mould 25 that contains features defined on its surface was used to emboss into the imprint resist layer 24 under controlled temperature and pressure conditions, as shown in Figures 30 and 31. The features may have the nano-scale sizes. The imprinting temperature was chosen to be Tg + 800C and the applied pressure was 50 kg cm-2. A very good pattern definition was reached. Thereby a thickness contrast in the imprint resist layer 24 was formed, as shown in Figure 32. This thickness contrast was further transferred through the imprint resist layer 24 via an O2 plasma-based anisotropic etching process. As a result, a patterned resist layer 26 has been formed, as shown in Figure 33. In the present example a hard mould was made of silicon; other materials selected from the list comprising SiO2, SiC, silicon nitride, sapphire, and diamond may be used for making the mould. The subsequent steps of formation of a pattern in the ribtan layer were carried out similarly to the Example 3, and as shown in Figures 21 and 22.
Example 7
Example 7 illustrates another embodiment of the patterning method with use of thermal imprint lithography. A layer comprising a water-based solution 27 of bis-carboxy DBI PTCA was applied on a substrate, as shown in Figure 34. The solution comprised a mixture of six isomers, as shown in Figure 1. Bis-carboxy DBI PTCA is a π-conjugated organic compound, where the predominantly planar carbon-conjugated core (CC in formula I) comprises rylene fragments, the benzimidazole groups serve as hetero-atomic groups, and carboxylic groups serve as substituents providing solubility. The molecular structure provides for the formation of rod-like molecular stacks. Quartz was used as a substrate material.
A hard mould 25 with the features on its surface was used to emboss into wet layer 27 under controlled temperature and pressure conditions, as shown in Figures 35 and 36. The features may be characterized with the nano-scale sizes. The imprinting temperature was chosen to remove solvent from the wet layer 27 and to form a solid layer 28 having a thickness contrast, as shown in Figures 36 and 37. This thickness contrast was further transferred through the solid layer 28 with the O2 plasma-based anisotropic etching process. The next step was annealing which was carried out in vacuum at approximately 65O0C for about 20 minutes. The duration and temperature of this step were selected so as to ensure partial pyrolysis of the organic compound with at least partial removing of substituents, hetero-atomic and solubility groups from the solid patterned layer, and forming predominantly planar graphene-like carbon-based structures on the basis of the carbon- conjugated residues. The patterned ribtan layer 29 has been formed on the substrate 2 as the result of annealing, as shown in Figure 38. Example 8
Example 8 illustrates another embodiment of the patterning method with use of reverse imprint lithography. If the mould feature has a high aspect ratio, then a different mode may be used for the forming of the patterns in the ribtan layer. The features may be of the nano-scale sizes.
A layer of the water-based solution 30 of bis-carboxy DBI PTCA was applied on the mould surface that contains nanoscale features, as shown in Figure 39. The solution comprised a mixture of six isomers as shown in Figure 1. Bis-carboxy DBI PTCA is a π- conjugated organic compound, where the predominantly planar carbon-conjugated core (CC as in formula I) comprises rylene fragments, the benzimidazole groups serve as hetero- atomic groups and carboxylic groups serve as substituents providing solubility. The molecular structure provides for the formation of rod-like molecular stacks. In this case, the layer of water-based solution 30 cannot planarize the mould surface, leaving undulations on the surface of the wet layer coated on the surface (see Figure 39). Then such a wet-layer- coated mould was brought into contact with a substrate under an applied pressure and at a temperature necessary for drying the water solution layer, as shown in Figure 40. At the next step, the water solution layer on top of the protrusion was transferred to the substrate 2, as shown in Figure 41. Finally, the patterned ribtan layer 31 has been formed on the substrate 2 as a result of annealing which was carried out in vacuum at approximately 65O0C for about 20 minutes, as shown in Figure 42. The duration and temperature of this step were selected so as to ensure partial pyro lysis of the organic compound with at least partial removing of substituents and hetero-atomic from the ribtan layer, and forming predominantly planar graphene-like carbon-based structures on the basis of the carbon- conjugated residues.
Example 9
The example illustrates another embodiment of the patterning method with use of imprint lithography. A layer of a water-based solution of bis-carboxy DBI PTCA was applied on a substrate 2. The solution comprised a mixture of six isomers as shown in Figure 1. Bis-carboxy DBI PTCA is a π-conjugated organic compound, where the predominantly planar carbon-conjugated core (CC in formula I) comprises rylene fragments, the benzimidazole groups serve as hetero-atomic groups and carboxylic groups serve as substituents providing solubility. The molecular structure provides for the formation of rod- like molecular stacks. Quartz was used as a substrate material.
The drying step was performed at room temperature and humidity of around 70%. By the end of the drying step, the produced solid layer 32 usually retains about 10% of the solvent (see Figure 43). A preheated mould 33 was brought into a contact with the surface of the solid layer 32, as shown in Figure 44, or into a close proximity with the surface. The hard mould 33 contains features defined on its surface. The features may be characterized by the nano-scale sizes.
In another embodiment of the present invention, the mould was heated up by the spiral heater 35 controlled by DC, AC or pulsed voltage, as shown in Figure 45. The heat from the mould caused local annealing of the ribtan material. The mould temperature was selected such to provide annealing of parts 34 of the solid layer 32, which were in contact with tops of the mould protrusions. In still another embodiment of the present invention, the pattern to be transferred onto a multilayer structure was formed on one surface of a block of electroconductive material forming the mould 33, and with the features on its surface. The mould was brought into contact with the surface of the multilayer structure or into close proximity with the surface, as shown in Figure 46. An electrode 36 was placed on the surface opposite to the multilayer structure. Electricity was passed through the mould and the multilayer structure to the electrode, creating local heating and annealing of the parts 34 of the layer of the ribtan material. The local heating and annealing could also be done with an electroconductive probe or array of probes, and optionally with an e-beam. Thus, duration and temperature of this step were selected so as to ensure partial pyrolysis of the organic compound with at least partial removal of substituents, and hetero-atomic groups from the parts 34 of the solid layer 32, forming predominantly planar graphene-like carbon-based structures on the basis of the carbon-conjugated residues. Finally, the patterned ribtan layer 37 has been formed on the substrate 2 as a result of annealing, as shown in Figure 47.
Example 10 Example 10 illustrates one embodiment of an integrated circuit made with the ribtan layer according to the present invention. Figures 48a and 48b show several simple integrated circuits which may be made by patterning of the ribtan layer, and having a source electrode 42 and a drain electrode 43, which are interconnected with a graphene-like carbon-based strip 44, which may be a graphene-like strip of nano-scale thickness.
The circuits were formed on a dielectric substrate 2. Figure 48a shows an integrated circuit made by one of the lithographic methods disclosed in the present invention. Figure 48b shows an integrated circuit made by one of thermal patterning methods disclosed in the present invention, wherein the area 45 was not exposed to a local annealing.
Example 11
Example 11 illustrates another embodiment of the integrated circuit made with the ribtan layer according to the present invention. Figures 49 (a, b) and 50 (a, b) show transistors which may be made by patterning of the ribtan layer, and having a source electrode 42 and a drain electrode 43, which are interconnected with a graphene-like carbon-based strip 44. As shown in Figures 49 (a, b) and 50 (a, b), the transistors may be made by disposing a gate 46 adjacent to the graphene-like carbon-based strip 44 so that the electron transport property of the graphene-like carbon-based strip 44 is changed when a bias voltage is applied to the gate so as to induce an electric field that interacts with the graphene-like carbon-based strip 44. Figures 49a and 50a show transistors made by one of the lithographic methods disclosed in the present invention. These transistors were formed on the dielectric substrate 2. Figures 49b and 50b show transistors made by one of the thermal patterning methods disclosed in the present invention, wherein the area 45 was not exposed to a local annealing.
Example 12
Example 12 illustrates another embodiment of the integrated circuit made with the ribtan layer according to the present invention. Figures 51a and 51b show directional couplers, each of which has one input electrode 47 and two output electrodes 48 and 49.
The directional couplers were formed on a dielectric substrate 2. Figure 51a shows the directional coupler made by one of the lithographic methods disclosed by the present invention. Figure 51b shows directional coupler made by one of thermal patterning methods disclosed in the present invention, wherein the area 45 was not exposed to a local annealing. Example 13
This example describes yet another embodiment of the integrated circuit made of ribtan layer according to the present invention. Figures 52a and 52b show interferometer configurations which may be made by patterning of the ribtan layer. The interferometer configurations have a source electrode 50 and a drain electrode 51 which are interconnected with a loop-like structure that has a first branch 52 and a spaced-apart second branch 53. A gate electrode 54 is disposed adjacent to the first branch 52 so that it is capable of exerting an electrical field substantially only on the first branch 52. The interference may be registered by a change in the source-to-drain current. The interferometer configurations were formed on the dielectric substrate 2. Figure 52a shows interferometer configuration made by one of the lithographic methods disclosed in the present invention. Figure 52b shows interferometer configuration made by one of the thermal patterning methods disclosed in the present invention, wherein the area 45 was not exposed to a local annealing.
Example 14
This example describes another embodiment of the integrated circuit made of ribtan layer according to the present invention. Figures 53a and 53b show multi-gate interferometer configurations which may be made by patterning of the ribtan layer. The multi-gate interferometer configurations have a source electrode 55 and a drain electrode 56 which are interconnected with a loop-like structure that has a first branch 57 and a spaced- apart second branch 58. Several gate electrodes 59, 60, and 61 are disposed adjacent to the first branch 57 so that they are capable of exerting an electrical field substantially only on the first branch 57. The interference may be registered by the change in the source-to-drain current. The multi-gate interferometer configurations were formed on the dielectric substrate 2. Figure 53a shows multi-gate interferometer configuration made by one of the lithographic methods disclosed by the present invention. Figure 53b shows multi-gate interferometer configuration made by one of thermal patterning methods disclosed by the present invention, where the area 45 was not exposed to a local annealing.
Example 15
This example describes a method of formation of the multilayer structure with two ribtan layers patterned by the disclosed methods. The multilayer structure comprising substrate 65 and ribtan layer 66 with an additional layer of silicon dioxide 67 was formed as described in Example 1 or Example 2, as shown in Figure 54. Figures 54-72 illustrate this embodiment of the present invention during various patterning steps. The first step of the patterning was formation of a resist layer on the multilayer structure. The multilayer structure was placed in a clean room, which was illuminated with yellow light, since photoresist is not sensitive to wavelengths greater than approximately 0.5 μm. To ensure satisfactory adhesion of the resist the surface of the multilayer structure was pre-treated. The treatment has changed the surface of the multilayer structure from hydrophilic to hydrophobic. This change was made by the application of an adhesion promoter, which can provide a chemically compatible surface for the resist. After the application of this adhesion layer, the multilayer structure was held on a vacuum spindle, and a liquid resist was applied to the center of the multilayer structure. The structure was then rapidly accelerated up to a constant rotational speed, which was maintained for about 40 second. Spin speed was generally in the range of 1000 - 10000 rpm in order to coat a uniform photoresist layer about 0.5 to 1 μm thick. Figure 55 shows schematically the multilayer structure coated by the photoresist layer 68. As would be known to one skilled in the art, many variations may be used as methods of coating of the multilayer structure with the resist layer. Spray coating, flooding, electrostatic method, and any other methods known in the art may be used. A positive resist was used for the pattern formation step. After the spinning step, the multilayer structure was exposed to a soft bake (at approximately 90° - 12O0C for 60 - 120 second) in order to remove the solvent from the photoresist layer and to increase adhesion of the photoresist to the multilayer structure.
The multilayer structure coated by the photoresist layer was aligned with respect to the mask in an optical lithographic system. The mask has a pattern corresponding to a desired functional structure, and the photoresist was exposed to UV light through the mask, as shown in Figure 56. Figure 56 shows schematically the multilayer structure comprising the substrate 65, the ribtan layer 66, and the silicon dioxide layer 67, the photoresist layer
68, and the mask 69. The mask 69 comprises the translucent or transparent regions 71, and the opaque regions 70. The exposed photoresist was dissolved in the developer. The photoresist development was done by flooding the exposed structure with the developer solution. The developed structure was then rinsed and dried. After the development step, a post-baking at approximately 100° - 18O0C was conducted in order to increase the adhesion of the patterned photoresist layer to the multilayer structure.
Figure 57 shows the resulting structure comprising the multilayer structure and patterned photoresist layer 72. The structure shown in Figure 57 was then put in an environment that provides etching of the exposed additional layer of silicon dioxide 67 but does not attack the patterned photoresist 72. Figure 58 shows the multilayer structure with patterned additional layer of silicon dioxide 73. After that the photoresist was stripped (see Figure 59).
The patterned additional layer of silicon dioxide 73 has been used as a mask for the subsequent processing. In one embodiment of the present invention, the structure shown in
Figure 59 was then put in an environment that provides etching of the exposed ribtan layer but does not attack the patterned additional layer of silicon dioxide 73 and the areas of ribtan layer covered by the patterned layer 73, as shown in Figure 60.
The next step of the patterning was a formation of the second resist layer 75 on the formed structure as shown in Figure 61.
The multilayer structure coated by the second photoresist layer 75 was aligned with respect to the mask in an optical lithographic system. The mask had a pattern corresponding to a desired functional structure, and the photoresist was exposed to UV light through the mask, as shown in Figure 62. Figure 62 shows schematically the multilayer structure comprising the substrate 65, the patterned ribtan layer 74, and the patterned silicon dioxide layer 73, the photoresist layer 75, and the mask. The mask comprises the first translucent or transparent regions 78, and the second opaque regions 77. The exposed photoresist was dissolved in the developer. The photoresist development was done by flooding the exposed structure with the developer solution. The developed structure was then rinsed and dried. After the development step, a post-baking at approximately 100° - 18O0C was conducted in order to increase the adhesion of the patterned photoresist layer to the multilayer structure.
Figure 63 shows the resulting structure comprising the multilayer structure and the patterned photoresist layer 79. The structure shown in Figure 63 was then put in an environment that provides etching of the exposed patterned additional layer of silicon dioxide 73 but does not attack the patterned photoresist 79. Figure 64 shows the multilayer structure with the additionally patterned layer of silicon dioxide 80. After that the photoresist was stripped, as shown in Figure 65. The following step of the patterning was a formation of the third resist layer 81 on the formed structure as shown in Figure 66.
The multilayer structure coated by the third photoresist layer 81 was aligned with respect to the mask in an optical lithographic system. The mask had a pattern corresponding to a desired functional structure, and the photoresist was exposed to UV light through the mask 82, as shown in Figure 67. Figure 67 schematically shows the multilayer structure comprising the substrate 65, the patterned ribtan layer 74, and the twice patterned silicon dioxide layer 80, the photoresist layer 81, and the mask 82. The mask 82 comprised the first translucent or transparent regions 84, and the opaque regions 83. The exposed photoresist was dissolved in the developer. The photoresist development was done by flooding the exposed structure with the developer solution. The developed structure was then rinsed and dried. After the development step, a post-baking at approximately 100° - 18O0C was conducted in order to increase the adhesion of the patterned photoresist layer to the multilayer structure. Figure 68 shows the resulting structure comprising the multilayer structure and the patterned third photoresist layer 81 with the opened windows 82. After that, a wet layer 83 comprising a water-based solution of bis-carboxy DBI PTCA was applied on the formed structure, as shown in Figure 69. Then the wet layer was dried. Figure 70 shows the dried layer 84 located on the top of the multilayer structure. As a result of removal of the resist layer 81 the patterned dried layer 85 has been formed, as shown in Figure 71. The next step was annealing of the dried patterned layer 85 which was carried out in vacuum at approximately 65O0C for about 20 minutes. The duration and temperature of this step were selected so as to ensure partial pyrolysis of the organic compound with at least partial removal of substituents and hetero-atomic groups from the solid patterned layer, forming predominantly planar graphene-like carbon-based structures on the basis of the carbon- conjugated residues. The patterned ribtan layer 86 on the formed structure has been formed as the result of annealing, as shown in Figure 72.
Example 16 The example describes synthesis of bis(carboxybenzimidazoles) of perylene tetracarboxylic acid (rylene fragments ## 4 and 5 in Table 1):
Mixture of 3,4,9,10-perylenetetracarboxylic-3,4:9,10-dianhydride (10 g) and 3,4- diaminobenzoic acid (39 g) was agitated in N-methylpyrrolidone (250 ml) for 6 hours at 175-1800C. Self cooled reaction mass was filtered. Filter cake was rinsed with N- methylpyrrolidone and dissolved in a mixture of water (1500 ml) and concentrated ammonia solution (100 ml). Dimethylformaide (1 L) was added to the solution. Precipitate was filtered and rinsed with dimethylformaide. Filter cake was suspended in water (1 L). Concentrated hydrochloric acid (100 ml) was added and precipitate was filtered. Then the filter cake was suspended in -500 ml of water, filtered and rinsed with water. Yield 13.2 g.
Example 17
The example describes synthesis of diphenylimide of 3,4,9,10- perylenetetracarboxylic acid (rylene fragment # 19 in Table 1):
Mixture of 3,4,9, 10-perylenetetracarboxylic-3,4:9,10-dianhydride (40 g), aniline (38 ml), zinc chloride (21 g) and ethylene glycol (400 ml) was agitated 8 hours at 180-1850C. After self cooling a precipitate was filtered and rinsed with hot water (1 L). Filter cake was agitated in 1% solution of potassium hydroxide for 2 hours. Precipitate was filtered and rinsed with hot water (1 L). Filter cake was agitated in a 2% solution of hydrogen chloride for 1 hour at 900C. Precipitate was filtered and rinsed with hot water (1 L). Filter cake was agitated in 1% solution of potassium hydroxide for 2 hours. Precipitate was filtered and rinsed with hot water (1 L). Filter cake was agitated in a 2% solution of hydrogen chloride for 1 hour at 900C. Precipitate was filtered and rinsed with hot water (1 L) and dried at 1000C. Yield 38.3 g.
Example 18 The example describes synthesis of dicarboxymetylimide of perylentetracarboxylic acid (carboxylic acid of base rylene fragment 10 in the Table 1)
Mixture of 3, 4,9,10-perylenetetracarboxylic-3, 4:9,10-dianhydride (2 g) and glycine (3.8 g) was agitated in the boiling N-methylpyrrolidone (50 ml) for 6 hours. A self cooled reaction mass was filtered. Filter cake was rinsed with N-nethylpyrrolidone, hydrochloric acid and water. Obtained filter cake was suspended in -300 ml of water, filtered and rinsed with water. Yield 0.73 g.
Example 19 The example describes synthesis of violanthrone disulfonic acid (anthrone fragment
# 24 in Table 2):
Violanthrone (10 g) was added to chlorosulfonic acid (50 ml) at ambient conditions. Then reaction mass was agitated at 85-900C for 15 hours. After self cooling a reaction mass was added by parts into water (600 ml). Precipitate was filtered and rinsed with water until filtrate became colored. Filter cake was agitated in the boiling water (500 ml) for two hours. The product was precipitated by addition of concentrated hydrochloric acid (600 ml). Precipitate was filtered, washed with 6 N hydrochloric acid (200 ml) and dried in oven (~100°C). Yield 11.8 g.
Example 20 The example describes synthesis of isoiolanthrone disulfonic acid (anthrone fragment # 25 in Table 2):
Isoviolanthrone (10 g) was charged into chlorosulfonic acid (50 ml) at ambient conditions. Then reaction mass was agitated at 85-900C for 16 hours. After self cooling a reaction mass was added into water (600 ml) by portions. Filter cake was agitated in the boiling water (600 ml) for 3 hours. The obtained hot solution was filtered through fiber glass filters. The substance was precipitated by addition of concentrated hydrochloric acid (550 ml). Precipitate was filtered, washed with 4 N hydrochloric acid (200 ml). Filter cake was suspended in 300 ml of 4 N hydrochloric acid. Precipitate was filtered, washed with 4 N hydrochloric acid (100 ml) and dried in oven (~100°C). Yield 7.5 g
Example 21
The example describes synthesis of decacyclene (polycyclic hydrocarbon fragment # 33 in Table 3):
Mixture of sulfur powder (10 g), acenaphthene (31 g) and potassium hydroxide (0.4 g) was heated at 230-3000C for 7 hours. Obtained fusion cake was ground and agitated in the boiling tetrachloroethane (200 ml) for 4 hours. Suspension was filtered at ~80°C. Filter cake was agitated in the boiling tetrachloroethane (200 ml) for 2 hours. Cooled suspension was filtered. Filter cake was rinsed with tetrachloroethane and suspended in hot N- methylpyrrolidone (300 ml, ~150°C). Cooled suspension was diluted with isopropanol (400 ml) and a precipitate was filtered. Filter cake was suspended in hot N-methylpyrrolidone (400 ml, ~150°C). Cooled suspension was filtered. Filtrate was diluted with water (1.5 L). Obtained precipitate was filtered, rinsed with water and dried at ~100°C. 11.2 g of dry powder were prepared. Filtrate (N-methylpyrrolidone - isopropanol) was diluted with water (1 L). Precipitate was filtered, rinsed with water and dried at ~100°C. 1.18 g of dry powder was prepared.
Obtained powder was combined and agitated in a boiling tetrachloroethane (70 ml) for 2 hours. Cooled suspension was filtered. Filter cake was rinsed with tetrachloroethane and chloroform.
Obtained powder (10.8 g) was suspended in hot N-methylpyrrolidone (400 ml, ~150°C). Cooled suspension was diluted with water (1 L). Obtained precipitate was filtered, rinsed with water and dried at ~100°C. Yield 6.5 g
Example 22
The example describes synthesis of decacyclene trisulfonic acid (polycyclic hydrocarbon fragment # 33 in Table 3):
Decacyclene (1 g) was charged into chlorosulfonic acid (5 ml) at ambient conditions. During charging hydrogen chloride was liberating. Then reaction mass was agitated at the room temperature for 48 hours. Then reaction mass was added into water (50 ml) by portions. Precipitate was filtered. Filter cake was agitated in water (100 ml) at ambient conditions and in hot water (800C) for 2 hours. Prepared solution was filtered through fiber glass filter. Filtrate was diluted with concentrated hydrochloric acid (100 ml) and dried at ~100°C. Yield 1.13 g.
Example 23
The example describes synthesis of truxene (polycyclic hydrocarbon fragment # 32 in Table 3):
1-Indanone (5.0 g) was inserted into a mixture of acetic acid (22 mL) and concentrated hydrochloric acid (11 mL). The resultant solution was agitated at 95-97° C for 16 houirs. Color turned yellow, bulky precipitate formed. The precipitate was filtered off, the solid material was washed with water (2x100 mL) and with acetone (100 mL, cold 5- 7°C). Yield 3.2 g
Example 24
The example describes synthesis of truxene trisulfonic acid (polycyclic hydrocarbon fragment # 32 in Table 3):
Truxene (3.4 g) was charged into oleum (80 mL, 4 %), slowly for 15 min trying to keep particles of the substance as fine as possible. The outer water bath was used to insure the room temperature of reaction mixture. Reaction mass was agitated for 5 hours. After that it was added dropwise into ice (135 g). Pale-creme precipitate was diluted with concentrated hydrochloric acid (150 mL), stirred overnight, filtered off, then washed with concentrated hydrochloric acid (150 mL), water (60 mL) and the resultant solution was diluted with 36% hydrochloric acid (150 mL). A jelly brown-green jelly precipitate was formed, solution was removed, and a fresh portion of hydrochloric acid was added (150 mL). Stirring was continued whereas a jelly mass turned to a solid precipitate. Then suspension was filtered, the solid material was washed with concentrated hydrochloric acid (50 mL), dried over wet sodium hydroxide, phosphorous oxide with mild heating. Yield 6.7 Example 25
Example describes preparation of N,N'-(l-undecyl)dodecyl-5,l l-dihexylcoronene- 2,3:8,9-tetracarboxydiimide (coronene fragment 49 in the Table 4). The preparation comprised 6 steps:
Commercially available perylene-3,4:9,10-tetracarboxylic dianhydride (100.0 g, 0.255 mol) was brominated with mixture of bromine (29 mL) and iodine (2.38 g) in 100% sulfuric acid (845 mL) at.~ 85° C. The yield of 1,7-Dibromoperylene-3,4:9,10- tetracarboxylic dianhydride was 90 g (64%).
Analysis: calculated: C24H6Br2O6, C 52.40, H 1.10, Br 29.05, O 17.45 %; found: C 52.29, H, 1.07, Br 28, 79 %. Absorption spectrum (9.82xlO~5 M solution in 93% sulfuric acid): 405 (9572), 516 (27892), 553 (37769).
N,N'-Dicyclohexyl- 1 ,7-dibromoperylene-3 ,4:9,10-tetracarboxydiimide was synthesized by the reaction of l,7-dibromoperylene-3,4:9,10-tetracarboxylic dianhydride (30.0 g) with cyclohexylamine (18.6 mL) in N-methylpyrrolidone (390 mL) at ~85 ° C.
The yield of N^'-dicyclohexyl-lJ-dibromoperylene-S^^lO-tetracarboxydiimide was 30 g (77%).
N,N'-Dicyclohexyl- 1 ,7-di(oct- 1 -ynyl)perylene-3 ,4:9,10-tetracarboxydiimide was synthesized by Sonagashira reaction: N,N'-dicyclohexyl-l,7-dibromperylene-3,4:9,10- tetracarboxydiimide (24.7 g) and octyne-1 (15.2 g) in the presence of bis(triphenylphosphine)palladium(II) chloride (2.42 g), triphenylphospine (0.9 g),and copper(I) iodide (0.66 g). The yield of N,N'-dicyclohexyl-l,7-di(oct-l-ynyl)perylene- 3,4:9,10-tetracarboxydϋmide was 15.7 g (60 %). N,N'-dicyclohexyl-5,l l-dihexylcoronene-2,3:8,9-tetracarboxydiimide was synthesized by the heating of N,N'-dicyclohexyl-l,7-di(oct-l-ynyl)perylene-3,4:9,10- tetracarboxydiimide (7.7 g) in toluene (400 mL) in the presence of 1,8-diazabicyclo [5.4.0]undec-7-ene (0.6 ml) at 100-110° C for 20 hours.
5,l l-dihexylcoronene-2,3:8,9-tetracarboxylic dianhydride was prepared by hydrolysis of N,N'-dicyclohexyl-5,l l-dihexylcoronene-2,3:8,9-tetracarboxydiimide (6.4 g,
8.3 mmol) with potassium hydroxide (7.0 g, 85%) in the mixture of tert-butanol (400 mL) and water (0.4 mL) at 85-900C. The yield of 5,l l-dihexylcoronene-2,3:8,9-tetracarboxylic dianhydride was 4.2 g (83%).
N,N'-( 1 -undecyl)dodecyl-5 , 11 -dihexylcoronene-2,3 : 8,9-tetracarboxydiimide was synthesized by the reaction of 5,l l-di(hexyl)coronene-2,3:8,9-tetracarboxylic dianhydride with 12-tricosanamine.
5,l l-di(hexyl)coronene-2,3:8,9-tetracarboxylic dianhydride (3.44 g), 12- tricosanamine (7.38 g), benzoic acid (45 mg) and 3-Chlorophenol (15 mL) were evacuated and saturated with argon two times at room temperature and then two times at 1000C. The reaction mixture was agitated at ~140°C for 1 hour and 160-1650C for 20 hours in a flow of argon. After that the reaction mixture was agitated at ~100°C and was vacuumed at 10 mm Hg for half an hour. Then apparatus was filled with argon once again and heating was continued for the next 24 hours. A drop of reaction mixture was mixed with acetic acid (5 mL), centrifuged, solid was dissolved in chloroform (0.5 mL) which was washed with water and dried over sodium sulfate. Thin layer chromatography probe showed good formation of product with Rf 0.9 (eluent: chloroform-hexane-ethylacetate-methanol (100:50:0.3:0.1 by V)).
The reaction mixture was added in small portions to acetic acid (500 mL) with simultaneous shaking. The orange-red suspension was kept for 3 hours with periodic shaking, then filtered off. The filter cake was washed with water (0.5 L), and then was shaken with water (0.5 L) and chloroform (250 mL) in a separator funnel. The organic layer was separated, washed with water (2x350 mL) and dried over sodium sulfate overnight. The evaporation resulted in 7.0 g of crude product. Column chromatography was carried out using exactly tuned eluent mixture: chloroform (700 mL), petroleum ether (2 L), ethylacetate (0.6 mL) and methanol (0.2). Column chromatography was carried out using column: 1 = 20, d = 7 cm. Elution of orange fraction and evaporation resulted in orange soft solid material, which was dissolved in chloroform (25 mL) and added slowly to methanol (400 mL) with agitation. The soft precipitate was dried on air overnight, then in vacuum (15 mm Hg) at mild heating (35°) for 5 hours. The yield of preparation of N,N'-(l-undecyl)dodecyl-5,l l-dihexylcoronene- 2,3:8,9-tetracarboxydiimide was 5.O g (70%).
The above described embodiments are given as illustrative examples only. It will be readily appreciated that many deviations may be made from the specific embodiments disclosed in this specification without departing from the invention. Accordingly, the scope of the invention is to be determined by the claims below rather than being limited to the specifically described embodiments above.

Claims

CLAIMSWhat is claimed is:
1. A method of lithography patterning, comprising: a) formation of a ribtan layer, comprising the sequence of following steps: (i) application of a solution on a substrate, wherein the solution comprises at least one π-conjugated organic compound of general structural formula I or a combination of organic compounds of the general structural formula I:
where CC is a predominantly planar carbon-conjugated core;
A is a hetero-atomic group; p is O, 1, 2, 3, 4, 5, 6, 7, or 8; S1, S2, S3 and S4 are substituents; ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8; and sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8;
(ii) drying with formation of a solid precursor layer; and
(iii) annealing with formation of an electrical-conducting ribtan layer comprising graphene-like carbon-based structures, wherein said annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound(s) with at least partial removal of the hetero-atomic groups and the substituents from the layer, and 2) fusion of carbon- conjugated residues in order to form predominantly planar graphene-like carbon-based structures; and b) formation of a patterned electrical-conducting ribtan layer by lithography, comprising the steps of: (iv) formation of a resist layer on the electrical-conducting ribtan layer; (v) formation of a pattern in the resist layer; and
(vi) transfer of the pattern from the resist layer to the electrical-conducting ribtan layer.
2. A method according to Claim 1, wherein the step (a) of the electrical-conducting ribtan layer formation further comprises a formation of at least one additional layer after the annealing step (iii), wherein the additional layer comprises a dielectric material, semiconductor material, metal or any combination thereof, and wherein the dielectric material is formed from an insulating material selected from the list comprising an insulating ribtan material, silicon dioxide (SiO2), silicon nitride (Si3N4), aluminum oxide (AI2O3), hafnium oxide (HfO2), zirconium silicate, hafnium silicate, hafnium silicate oxynitride, titanium oxide, tantalum oxide, alumsilicate, carbon, carbon-doped silicon dioxide, and combination thereof; and the metal is selected from the list comprising copper, gold, silver, zinc, tin, indium, aluminum, titanium, poly-silicon, ribtan layer as a semi-metal conductor, and any combination thereof.
3. A method according to any of Claims 1 or 2, wherein the substrate is made of one or several materials of the list comprising Si, Ge, SiGe, GaAs, diamond, quartz, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, metals, and any combination thereof, wherein the substrate further comprises doped regions, circuit features, multilevel interconnects, and at least one said patterned electrical-conducting ribtan layer.
4. A method according to any of Claims 1 to 3, wherein the electrical-conducting ribtan layer possesses anisotropy of conductivity and/or an optical anisotropy.
5. A method according to any of Claims 1 to 4, wherein the graphene-like carbon-based structures are globally ordered on the substrate surface.
6. A method according to any of Claims 1 to 5, wherein the electrical-conducting ribtan layer possesses conductivity selected from the list comprising semiconductor conductivity of n-type, semiconductor conductivity of p-type, and electric conductivity approximating to metal-type conductivity.
7. A method according to any of Claims 1 to 6, wherein the graphene-like carbon-based structures have the form selected from the list comprising disk, plate, lamella, ribbon, and any combination thereof and a distance between planes of the graphene-like carbon-based structures approximately equals to 3.5 ± 0.1 A.
8. A method according to any of Claims 1 to 7, wherein said organic compound comprises one or more rylene fragments, and has a general structural formula selected from the list comprising structures 1-23:
9. A method according to any of Claims 1 to 7, wherein said organic compound comprises one or more anthrone fragments and has a general structural formula selected from the list comprising structures 24-31 :
10. A method according to any of Claims 1 to 7, wherein said organic compound comprises planar fused polycyclic hydrocarbon, and wherein said organic compound comprising planar fused polycyclic hydrocarbon is selected from the list comprising truxene, decacyclene, antanthrene, hexabenzotriphenylene, 1.2,3.4,5.6,7.8-tetra-(peri-naphthylene)- anthracene, dibenzoctacene, tetrabenzoheptacene, peropyrene, hexabenzocoronene, violanthrene, isoviolanthrene and has a general structural formula selected from the list comprising structures 32-43:
11. A method according to any of Claims 1 to 7, wherein said organic compound comprises one or more coronene fragments and has a general structural formula selected from the list comprising structures 44 - 51 :
12. A method according to any of Claims 1 to 11, wherein at least one of the hetero-atomic groups A is selected from the list comprising imidazole group, benzimidazole group, amide group, substituted amide group, and hetero-atom selected from nitrogen, oxygen, and sulfur.
13. A method according to any of Claims 1 to 12, wherein at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in water or aqueous solution and is selected from the list comprising COO , SO3 , HPO3 , and PO3 2 and any combination thereof.
14. A method according to any of Claims 1 to 12, wherein at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in the organic solvent and is selected from the list comprising (Ci-C35)alkyl, (C2-C3s)alkenyl, and (C2-C3s)alkinyl, CONR1R2, CONHCONH2, SO2NR1R2, R3, structures 52-58 or any combination thereof, wherein R1, R2 and R3 are selected from hydrogen, an alkyl group, an aryl group, and any combination thereof, where the alkyl group has the general formula -(CH2)nCH3, where n is an integer from O to 27, and the aryl group is selected from the list comprising phenyl, benzyl and naphthyl, where R is selected from the list, comprising linear or branched (C1- C35) alkyl, (C2-C35)alkenyl, and (C2-C35)alkinyl:
15. A method according to any of Claims 1 to 14, wherein the organic compound is capable of forming rod-like supramolecules in the solution via π-π- interaction between the adjacent carbon-conjugated cores.
16. A method according to Claim 15, further comprising an application of an external alignment action upon the applied solution, wherein the application and alignment steps are carried out simultaneously or the alignment step is carried out after the application step and the rod-like supramolecules are aligned in the substrate plane.
17. A method according to any of Claims 1 to 16, wherein at least one of the substituents S1, S2, S3 and S4 is a molecular binding group which number and arrangement provide for the formation of supramolecules from the organic compound molecules in the solution via non- covalent chemical bonds, and wherein at least one said binding group is selected from the list comprising hetero-atoms, COOH, SO3H, H2PO3, NH, NH2, CO, OH, NHR, NR, COOMe, CONH2, CONHNH2, SO2NH2, -SO2-NH-SO2-NH2 and any combination thereof, a hydrogen acceptor (AH), a hydrogen donor (DH), and a group having a general structural formula II
wherein the hydrogen acceptor (AR) and hydrogen donor (DR) are independently selected from the list comprising NH-group, and oxygen (O), radical R is an alkyl group or an aryl group, the alkyl group having the general formula -(CH2)nCH3, where n is an integer from O to 27, and the aryl group being selected from the list comprising phenyl, benzyl and naphthyl, wherein the non-covalent chemical bonds are independently selected from the list comprising a single hydrogen bond, dipole-dipole interaction, cation - pi-interaction, Van- der-Waals interaction, coordination bond, ionic bond, ion-dipole interaction, multiple hydrogen bond, interaction via the hetero-atoms and any combination thereof, and wherein the supramolecules are predominantly oriented in the plane of the substrate.
18. A method according to any of Claims 1 to 17, wherein the drying (ii) and annealing (iii) steps are carried out simultaneously or sequentially.
19. A method according to any of Claims 1 to 17, wherein the lithographic method is a photolithographic method, wherein the resist layer is a positive or negative photoresist layer, and wherein the formation of the photoresist layer comprises the following steps: (vii) treatment of the electrical-conducting ribtan layer; (viii) coating of the photoresist layer by one or several methods selected from the list comprising spin coating, spray coating, flooding, and electrostatic method; and (ix) soft baking.
20. A method according to Claim 19, wherein the formation of the pattern in the photoresist layer comprises the following steps: (x) alignment of a mask with the electrical-conducting ribtan layer; (xi) exposure of the photoresist layer by means of light radiation through the mask; (xii) development of the photoresist layer; and (xiii) rinsing and drying of the electrical-conducting ribtan layer and post-baking of the patterned photoresist layer and wherein the formation of the pattern in the photoresist layer further comprises a soft baking step after the exposure step (xi), wherein the exposure step (xi) is carried out by means of an ultraviolet radiation, wherein a spectral range is defined by the photoresist used.
21. A method according to Claim 20, wherein the exposure step (xi) is carried out by means of a printing technique selected from the list comprising a contact printing which is applied to the entire wafer, wherein the electrical-conducting ribtan layer is brought into the surface contact with the mask, a proximity printing which is applied to the entire electrical- conducting ribtan layer, wherein there is a gap between the electrical-conducting ribtan layer and the mask, and a projection printing which is applied only to portions of the electrical-conducting ribtan layer, wherein there is a gap between the electrical-conducting ribtan layer and the mask.
22. A method according to any of Claims 19 to 21, wherein the transfer step further comprises the following steps: (xiv) etching of the electrical-conducting ribtan layer, wherein said layer is located underneath the patterned photoresist layer; and (xv) removing of the patterned photoresist layer, wherein the etching technique is selected from a wet etching and a dry-etching method, wherein the dry-etching method is selected from the list comprising plasma etching, reactive ion etching (RIE), sputter etching, magnetically enhanced RIE (MERIE), reactive ion beam etching, high-density plasma etching, and any combination thereof.
23. A method according to any of Claims 19 to 22, wherein the mask is a phase-shifting mask.
24. A method according to any of Claims 1 to 18, wherein the patterning lithographic method is an electron-beam projection lithographic method, wherein the resist layer is an electron resist layer, wherein the formation of the electron resist layer comprises the following steps: (xvi) treatment of the electrical-conducting ribtan layer in order to clean said electrical-conducting ribtan layer and increase an adhesion of the electron resist layer to the electrical-conducting ribtan layer; (xvii) coating of the electron resist layer by one or several methods selected from the list comprising spin coating, spray coating, flooding, and electrostatic method; and (xviii) drying of the electron resist layer, and wherein the electron resist is a positive or negative electron resist and wherein the formation of the pattern in the electron resist layer comprises the following steps: (xix) alignment of the mask with the electrical-conducting ribtan layer; (xx) exposure of the electron resist layer by means of electron-beam radiation through the mask; (xxi) development of the electron resist layer; and (xxii) rinsing and drying of the electrical-conducting ribtan layer and post-baking of the patterned electron resist layer.
25. A method according to Claim 24, wherein the transfer step further comprises the following steps: (xxiii) etching of the electrical-conducting ribtan layer, wherein the ribtan layer is located underneath the patterned electron resist layer; and (xxiv) removing of the patterned electron resist layer, wherein the etching technique is selected from a wet etching and a dry-etching method, and wherein the dry-etching is selected from a list comprising plasma etching, reactive ion etching (RIE), sputter etching, magnetically enhanced RIE (MERIE), reactive ion beam etching, high-density plasma etching, and any combination thereof.
26. A method according to any of Claims 24 or 25, wherein the mask is an electron scattering mask.
27. A method according to any of Claims 1 to 18, wherein the patterning lithographic method is an extreme-ultraviolet lithographic method, wherein the resist layer is a photoresist layer, wherein the spectral range of extreme-ultraviolet radiation is approximately from 10 to 14 nanometers and determined by the photoresist used.
28. A method according to Claim 27, wherein the formation of the patterned photoresist layer further comprises a reflection mask.
29. A method according to any of Claims 1 to 18, wherein the lithographic method is an imprint photolithographic method and the resist layer is an imprint resist layer, and wherein the formation of the imprint layer comprises the following steps: - treatment of the electrical-conducting ribtan layer in order to clean said electrical-conducting ribtan layer and increase adhesion of the imprint resist layer to the electrical-conducting ribtan layer; - coating of the imprint resist layer by one or several methods selected from the list comprising spin coating, spray coating, flooding, and electrostatic method; and - drying of the imprint resist layer.
30. A method according to Claim 29, wherein the imprint resist is a thermal plastic material.
31. A method according to any of Claims 29 or 30, wherein the formation of the pattern in the imprint resist layer comprises following steps: - formation of a thickness contrast in the imprint resist layer, wherein a hard mould that contains features defined on its surface is used to emboss into imprint resist layer under controlled temperature and pressure conditions; and - formation of a patterned resist layer, wherein the thickness contrast is transferred through the imprint resist layer via an anisotropic etching process, wherein the hard mould is made of materials selected from the list comprising silicon, silicon dioxide, silicon carbide, silicon nitride, sapphire, and diamond, and wherein the features are characterized with nano-scale sizes.
32. A method according to any of Claims 1 to 31, wherein the at least one of the substituents S1, S2, S3 and S4 is selected from the list comprising -NO2, -Cl, -Br, -F, -CF3, - CN, -OCH3, -OC2H5, -OCOCH3, -OCN, -SCN, and -NHCOCH3.
33. A method of thermal patterning, comprising the following steps:
- application of a solution on a substrate,
wherein the solution comprising at least one π-conjugated organic compound of a general structural formula I or a combination of organic compounds of the general structural formula I:
where CC is a predominantly planar carbon-conjugated core; A is a hetero-atomic group; p is 0, 1, 2, 3, 4, 5, 6, 7, or 8; S1, S2, S3 and S4 are substituents; ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8; and sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8;
- drying with formation of a solid precursor layer, and
- formation of a pattern in the solid precursor layer by a local annealing, wherein said local annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound(s) with at least partial removal of the hetero-atomic groups and the substituents from the solid layer and 2) fusion of carbon-conjugated residues in order to form predominantly planar graphene-like carbon-based structures.
34. A method according to Claim 33, wherein the substrate is made of the material selected from the list comprising a heat-sensitive material, Si, Ge, SiGe, GaAs, diamond, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, and metals and any combination thereof and further comprises doped regions, circuit features, multilevel interconnects, and at least one patterned ribtan layer.
35. A method according to any of Claims 33 or 34, wherein said organic compound comprises one or more rylene fragments, and has a general structural formula selected from the list comprising structures 1-23:
36. A method according to any of Claims 33 or 34, wherein said organic compound comprises one or more anthrone fragments, and has a general structural formula selected from the list comprising structures 24-31 :
37. A method according to any of Claims 33 or 34, wherein said organic compound comprises planar fused polycyclic hydrocarbon, and wherein said organic compound comprising planar fused polycyclic hydrocarbons is selected from the list comprising truxene, decacyclene, antanthrene, hexabenzotriphenylene, 1.2,3.4,5.6,7.8-tetra-(peri- naphthylene)-anthracene, dibenzoctacene, tetrabenzoheptacene, peropyrene, hexabenzocoronene, violanthrene, isoviolanthrene and has a general structural formula from the list comprising structures 32 - 43:
38. A method according to any of Claims 33 or 34, wherein said organic compound comprises one or more coronene fragments, and has a general structural formula selected from the list comprising structures 44 - 51 :
39. A method according to any of Claims 33 to 38, wherein at least one of the hetero-atomic groups A is selected from the list comprising imidazole group, benzimidazole group, amide group, substituted amide group, and hetero-atom selected from nitrogen, oxygen, and sulfur.
40. A method according to any of Claims 33 to 39, wherein at least one of said substituents S1, S2, S3 and S4 provides solubility of the organic compound in water or aqueous solution and is selected from the list comprising COO , SO3 , HPO3 , and PO32 and any combination thereof.
41. A method according to any of Claims 33 to 39, wherein at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in organic solvents and is selected from the group comprising (Ci-C35)alkyl, (C2-C3s)alkenyl, and (C2-C3s)alkinyl, CONR1R2, CONHCONH2, SO2NR1R2, R3, structures 52-58 or any combination thereof, wherein R1, R2 and R3 are selected from hydrogen, an alkyl group, an aryl group, and any combination thereof, where the alkyl group has the general formula -(CH2)nCH3, where n is an integer from 0 to 27, and the aryl group is selected from the group comprising phenyl, benzyl and naphthyl, where R is selected from the group comprising linear or branched (C1- C35) alkyl, (C2-C35)alkenyl, and (C2-C35)alkinyl:
42. A method according to any of Claims 33 to 41, wherein the organic compound is capable of forming rod-like supramolecules in the solution via π-π- interaction between the adjacent carbon-conjugated cores, further comprising a step of the application of an external alignment action upon the applied solution in order to provide aligned orientation of the rod-like supramolecules, and wherein the application and alignment steps are carried out simultaneously or the alignment step is carried out after the application step, wherein the rod-like supramolecules are aligned in the substrate plane.
43. A method according to any of Claims 33 to 42, wherein at least one of the substituents S1, S2, S3 and S4 is a molecular binding groups which number and arrangement provide for the formation of supramolecules from the organic compound molecules in the solution via non-covalent chemical bonds, and wherein at least one said binding group is selected from the list comprising hetero-atoms, COOH, SO3H, H2PO3, NH, NH2, CO, OH, NHR, NR, COOMe, CONH2, CONHNH2, SO2NH2, -SO2-NH-SO2-NH2 and any combination thereof, a hydrogen acceptor (AR), a hydrogen donor (DR), and a group having the general structural formula
wherein the hydrogen acceptor (AH) and hydrogen donor (DH) are independently selected from the list comprising NH-group, and oxygen (O, where radical R is an alkyl group or an aryl group, the alkyl group having the general formula -(CH2)nCH3, where n is an integer from 0 to 27, and the aryl group being selected from the list comprising phenyl, benzyl and naphthyl, wherein the non-covalent chemical bonds are independently selected from the list comprising a single hydrogen bond, dipole-dipole interaction, cation - pi-interaction, Van- der-Waals interaction, coordination bond, ionic bond, ion-dipole interaction, multiple hydrogen bond, interaction via the hetero-atoms and any combination thereof and wherein the supramolecules are predominantly oriented in the plane of the substrate.
44. A method according to any of Claims 33 to 43, wherein at least one of the substituents S1, S2, S3 and S4 is selected from the list comprising -NO2, -Cl, -Br, -F, -CF3, -CN, -OCH3, - OC2H5, -OCOCH3, -OCN, -SCN, and -NHCOCH3.
45. A method according to any of Claims 33 to 44, wherein the local annealing is carried out by a technique selected from the list comprising a) a laser thermal patterning process using a one or several lasers a radiation technique selected from the list comprising electromagnetic radiation, X-ray, UV-radiation, infrared radiation, and any combination thereof, b) a focused ultrasound beam, c) a direct write technique, d) a heating element brought into contact with the surface of the solid layer or located into close proximity with the surface of the solid layer, wherein the heating element is a hard mould that contains features defined on its surface, wherein the features have nano-scale sizes, e) the sequence of following steps: - forming a patterned thermal-resist layer on the solid layer via one of lithographic methods; - exposing the thermal-resist layer to infrared radiation; and - removing the thermal-resist layer with one of the etch methods f) the sequence of following steps: - depositing metal lines on the surface of the solid layer; and - heating the metal lines and the surface by passing the electric current through said metal lines, g) the sequence of following steps: - forming a patterned resist layer on the solid layer via one of lithographic methods; - executing an exothermic chemical reaction on a surface of the solid layer; and - removing the resist layer with an etch method, h) by applying local pressure to the surface of the solid layer, wherein the local pressure to the surface is carried out by a hard mould that contains features defined on its surface, and wherein the features have nano-scale sizes, i) a technique selected from passing a current through at least one portion of the solid layer, wherein the passing of the current is carried out using the scanning tunneling microscope (STM) tip, array of STM tips, electron beam, array of electron beams, and any combination thereof, and by a DC, AC or pulsed electric current flowing between a hard mould made of electroconductive material, which comprises features defined on its surface and is brought into contact with the surface of the multilayer structure or into close proximity with the surface, and an electrode located on opposite surface of the multilayer structure, and wherein the features have nano-scale sizes.
46. A method according to any of Claims 33 to 45, wherein the local annealing is carried out using a pattern transfer mask-based technique.
47. A method of direct lithographic patterning, comprising the sequence of following steps: depositing a wet pattern on a substrate using a solution which comprises at least one π-conjugated organic compound of the general structural formula I or a combination of organic compounds of the general structural formula I:
where CC is a predominantly planar carbon-conjugated core; A is a hetero-atomic group; p is O, 1, 2, 3, 4, 5, 6, 7, or 8; S1, S2, S3 and S4 are substituents; and ml, m2, m3 and m4 are 0, 1, 2, 3, 4, 5, 6, 7, or 8; and sum (ml+m2+m3+m4) is 1, 2, 3, 4, 5, 6, 7, or 8;
- drying of said wet pattern with the formation of a solid pattern, and
- annealing with the formation of a solid pattern comprising graphene-like carbon-based structures and possessing electrical-conductivity, wherein said annealing is characterized by level of vacuum, composition and pressure of ambient gas, time dependence of annealing temperature and duration of exposure which are selected so as to ensure 1) partial pyro lysis of the organic compound with at least partial removal of hetero-atomic groups and substituents from the solid pattern and 2) fusion of the carbon-conjugated residues in order to form the predominantly planar graphene-like carbon-based structures.
48. A method according to Claim 47, wherein the substrate is made of one or several materials selected from the list comprising Si, Ge, SiGe, GaAs, diamond, quartz, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, metals and any combination thereof, wherein the substrate further comprises doped regions, circuit features, multilevel interconnects, and at least one patterned ribtan layer.
49. A method according to any of Claims 47 or 48, wherein said organic compound comprises one or more rylene fragments and has a general structural formula selected from the list comprising structures 1-23:
50. A method according to any of Claims 47 to 48, wherein said organic compound comprises one or more anthrone fragments and has a general structural formula selected from the list comprising structures 24-31 :
51. A method according to any of Claims 47 or 48, wherein said organic compound comprises planar fused polycyclic hydrocarbon, and wherein said organic compound comprising planar fused polycyclic hydrocarbons is selected from the list comprising truxene, decacyclene, antanthrene, hexabenzotriphenylene, 1.2,3.4,5.6,7.8-tetra-(peri- naphthylene)-anthracene, dibenzoctacene, tetrabenzoheptacene, peropyrene, hexabenzocoronene, violanthrene, isoviolanthrene and has a general structural formula selected from the list comprising structures 32 - 43:
52. A method according to any of Claims 47 or 48, wherein said organic compound comprises one or more coronene fragments and has a general structural formula selected from the list comprising structures 44 - 51 :
53. A method according to any of Claims 47 to 52, wherein at least one of the hetero-atomic groups A is selected from the list comprising imidazole group, benzimidazole group, amide group, substituted amide group, and hetero-atom selected from nitrogen, oxygen, and sulfur.
54. A method according to any of Claims 47 to 53, wherein at least one of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in water or aqueous solution and is selected from the list comprising COO , SO3 , HPO3 , and PO3 2- and any combination thereof.
55. A method according to any of Claims 47 to 53, wherein at least of the substituents S1, S2, S3 and S4 provides solubility of the organic compound in organic solvents and is selected from the list comprising (C1-C35)alkyl, (C2-C35)alkenyl, and (C2-C35)alkinyl, CONR1R2, CONHCONH2, SO2NR1R2, R3, structures 52-58or any combination thereof, wherein R1, R2 and R are selected from hydrogen, an alkyl group, an aryl group, and any combination thereof, where the alkyl group has the general formula -(CH2)nCH3, where n is an integer from O to 27, and the aryl group is selected from the list comprising phenyl, benzyl and naphthyl, where R is selected from the list comprising linear or branched (C ^35) alkyl, (C2-C35)alkenyl, and (C2-C35)alkinyl:
56. A method according to any of Claims 47 to 55, wherein the organic compound is capable of forming rod-like supramolecules in the solution via π-π- interaction between the adjacent carbon-conjugated cores, further comprising the step of application of an external alignment action upon the applied solution in order to provide aligned orientation of the rod-like supramolecules, and wherein the application and alignment steps are carried out simultaneously or the alignment step is carried out after the application step and wherein the rod-like supramolecules are aligned in the substrate plane.
57. A method according to any of Claims 47 to 56, wherein at least one of the substituents is a molecular binding groups which number and arrangement provide for the formation of supramolecules from the organic compound molecules in the solution via non- covalent chemical bonds, and wherein at least one said binding group is selected from the list comprising hetero-atoms, COOH, SO3H, H2PO3, NH, NH2, CO, OH, NHR, NR, COOMe, CONH2, CONHNH2, SO2NH2, -SO2-NH-SO2-NH2 and any combination thereof, a hydrogen acceptor (AH), a hydrogen donor (DH), and a group having the general structural formula
wherein the hydrogen acceptor (AR) and hydrogen donor (DR) are independently selected from the list comprising NH-group, and oxygen (O, where radical R is an alkyl group or an aryl group, the alkyl group having the general formula -(CH2)nCH3, where n is an integer from O to 27, and the aryl group being selected from the list comprising phenyl, benzyl and naphthyl, wherein the non-covalent chemical bonds are independently selected from the list comprising a single hydrogen bond, dipole-dipole interaction, cation - pi-interaction, Van- der-Waals interaction, coordination bond, ionic bond, ion-dipole interaction, multiple hydrogen bond, interaction via the hetero-atoms and any combination thereof and wherein the supramolecules are predominantly oriented in the plane of the substrate.
58. A method according to any of Claims 47 to 57, wherein at least one of the substituents S1, S2, S3 and S4 is selected from the list comprising -NO2, -Cl, -Br, -F, -CF3, - CN, -OCH3, -OC2H5, -OCOCH3, -OCN, -SCN, and -NHCOCH3.
59. A method according to any of Claims 47 to 58, wherein said solution is an isotropic solution or a lyotropic liquid crystal solution.
60. A method according to any of Claims 47 to 59, further comprising an alignment action, wherein the alignment action is carried out simultaneously with the application of said wet pattern on the substrate.
61. A method according to any of Claims 47 to 60, wherein the depositing step is carried out by at least one of techniques selected from the list comprising a printing with use of stamps, a reverse-imprinting, an ink-jet printing with use of nozzles, laser printing and imaging, a drawing by a ruling pen (drawing-pen), a dip-pen lithographic technique, drawing with use of masks and any combination thereof.
62. A method according to any of Claims 47 to 61, wherein the drying and annealing steps are carried out simultaneously or sequentially.
63. A method according to any of Claims 47 to 58, wherein the step of deposition of a wet pattern on a substrate comprises an application on a substrate of the solution comprising at least one π-conjugated organic compound of the general structural formula (I) and formation of a wet layer on the substrate; and an embossing into the wet layer of a hard mould that contains features defined on its surface and formation of a thickness contrast in the wet layer, and wherein the features have nano-scale sizes.
64. A method according to Claim 63, wherein the drying of the wet layer is carried out during pressing the hard mould to the wet layer and a solid layer with the thickness contrast is formed.
65. A method according to any of Claims 63 or 64, further comprising a step of transferring thickness contrast through the solid layer via an anisotropic etching process, wherein this step is carried out after the drying step.
66. An integrated circuit, comprising a ribtan layer on the substrate, wherein the ribtan layer is patterned according to any of Claims 1 to 65 to define at least one functional structure, and wherein the substrate is made of one or several materials of the list comprising an insulator, Si, Ge, SiGe, GaAs, diamond, silicon carbide, indium arsenide, indium phosphide, silicon germanium carbide, gallium arsenic phosphide, gallium indium phosphide, plastics, glasses, ceramics, metal-ceramic composites, metals and any combination thereof, wherein the substrate further comprises doped regions, circuit features, multilevel interconnects, and at least one patterned ribtan layer.
67. An integrated circuit according to Claim 66, wherein the ribtan layer comprises at least one structure from the list comprising a graphene-like structure of nano-scale thickness, graphene-like strip, graphene-like carbon-based strip, and any combination thereof.
68. An integrated circuit according to any of Claims 66 or 67, wherein the ribtan layer is patterned to form at least one electronic device, wherein the electronic device comprises a transistor, wherein the transistor comprises a source electrode, a drain electrode, spaced apart from the source electrode, a connector, in electrical communication with both the source electrode and the drain electrode; and a gate electrode spaced apart from the connector at a distance such that an electron transport property of the connector changes when bias voltage is applied to the gate electrode so as to induce a field that interacts with the connector, wherein the connector is made by patterning of the ribtan layer, wherein at least one electrode selected from the list comprising a source electrode, drain electrode and gate electrode comprises the ribtan layer.
69. An integrated circuit according to any of Claims 67 or 68, wherein the electronic device further comprises at least one element from the list comprising a logic gate, logic directional coupler, interferometer, and any combination thereof, wherein the interferometer comprises a source electrode, drain electrode, loop-like structure, having a first branch and a spaced- apart second branch, in electrical communication with the source electrode and with the drain electrode, at least one gate electrode disposed adjacent to the first branch, that is capable of exerting an electrical field substantially only on the first branch, and a sensor that may sense interference between electrons passing through the first branch and electrons passing through the second branch, wherein the loop-like structure is made by patterning of ribtan layer and wherein at least one electrode selected from the list comprising a source electrode, a drain electrode and a gate electrode comprises the ribtan layer.
70. An integrated circuit according to Claim 69, wherein the interferometer comprises a Mach-Zender device.
EP09771083A 2008-06-26 2009-06-26 Patterned integrated circuit and method of production thereof Withdrawn EP2311078A4 (en)

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