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WO2007117672A2 - Methods of depositing nanomaterial & methods of making a device - Google Patents

Methods of depositing nanomaterial & methods of making a device Download PDF

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Publication number
WO2007117672A2
WO2007117672A2 PCT/US2007/008721 US2007008721W WO2007117672A2 WO 2007117672 A2 WO2007117672 A2 WO 2007117672A2 US 2007008721 W US2007008721 W US 2007008721W WO 2007117672 A2 WO2007117672 A2 WO 2007117672A2
Authority
WO
WIPO (PCT)
Prior art keywords
accordance
nanomaterial
tape
substrate
composition
Prior art date
Application number
PCT/US2007/008721
Other languages
French (fr)
Other versions
WO2007117672A3 (en
Inventor
Marshall Cox
Leeann Kim
Craig Breen
Maria J. Anc
Seth Coe-Sullivan
Peter T. Kazlas
Original Assignee
Qd Vision, Inc.
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 Qd Vision, Inc. filed Critical Qd Vision, Inc.
Publication of WO2007117672A2 publication Critical patent/WO2007117672A2/en
Priority to US12/287,145 priority Critical patent/US9034669B2/en
Publication of WO2007117672A3 publication Critical patent/WO2007117672A3/en

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    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02601—Nanoparticles
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02603—Nanowires
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02606—Nanotubes
    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/166—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using selective deposition, e.g. using a mask
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/30—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant
    • B05D2401/32—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant applied as powders
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
    • H01L21/02639—Preparation of substrate for selective deposition
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Definitions

  • the invention relates to compositions and methods of depositing same. More particularly, the invention relates to compositions including nanomaterial, methods and systems for depositing same.
  • a number of industries e.g., electronics, displays, lighting, optoelectronics, and energy industries, rely on the formation of layers, coatings and/or patterns of materials to form pixels, circuits, and other features on substrates.
  • the primary methods for generating these patterns are screen printing for features larger than about 100 microns and thin film and etching methods for features smaller than about 100 microns.
  • Other subtractive methods to attain fine feature sizes include the use of photo-patternable pastes and laser trimming.
  • a method for depositing nanomaterial onto a substrate comprises applying a composition comprising nanomaterial to a surface of a tape, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate.
  • a method for depositing nanomaterial onto a substrate comprises applying a composition comprising nanomaterial to a surface of a tape from a transfer surface, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate.
  • the nanomaterial can be included in a composition which may or may not include further components.
  • the composition can further include a liquid or other carrier medium.
  • the composition can optionally include one or more additional components.
  • a nanomaterial typically includes nanoparticles having an average maximum dimension smaller than 100 nm. Examples of nanoparticles include, for example, a semiconductor nanocrystal, a nanotube (such as a single walled or multi-walled carbon nanotube), a nanowire, a nanorod, a dendrimer, organic nanocrystal, organic small molecule, other nano-scale or micro-scale material or mixtures thereof.
  • nanomaterial includes semiconductor nanocrystals.
  • Semiconductor nanocrystals comprise nanometer-scale inorganic semiconductor particles.
  • Semiconductor nanocrystals preferably have an average nanocrystal diameter less than about ISO Angstroms (A), and most preferably in the range of 12-150 A.
  • a method of making a light emitting device comprises applying a composition comprising semiconductor nanocrystals to a surface of a tape, and contacting the surface of the tape including the semiconductor nanocrystals to the substrate under conditions to cause at least a portion of the semiconductor nanocrystals to deposit onto the substrate.
  • a method of forming a device comprises applying a composition comprising nanomaterial to a surface of a tape; contacting the surface of the tape including the nanomaterial to a substrate a substrate including a first electrode under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate; and arranging a second electrode opposed to the first electrode.
  • the tape including nanomaterial can be divided into sheets of predetermined size prior to being contacted to the substrate.
  • the size of the sheet corresponds to the size of the substrate onto which nanomaterial is to be deposited.
  • the size of the sheet corresponds to the size of a predetermined area of the substrate onto which nanomaterial is to be deposited.
  • Other aspects of the invention include systems and articles for transferring a nanomaterial to a surface.
  • FIGS. 1 A-B are diagrams depicting examples of an embodiment of a transfer surface including a pattern of grooves.
  • FIGS. 2 A-B are diagrams depicting examples of embodiments including a mask.
  • FIG. 3 is a diagram depicting an example of a technique for dispensing one or more compositions to a transfer surface.
  • FIG. 4 illustrates an example of a technique for dispensing one or more compositions to a transfer surface.
  • FIG. S is a diagram depicting an example of a method of the invention including a tape.
  • FIG. 6 are diagrams depicting examples of applicators for use in various embodiments of a method of the invention.
  • FIG. 7 is diagram depicting an example of a system for use in various embodiments of a method of the invention.
  • FIGS. 8 A-D are diagrams depicting an example of a system including a transfer surface and tape for use in various embodiments of a method of the invention.
  • FIG. 9 is a diagram depicting an example of a system including a tape for use in various embodiments of a method of the invention.
  • FIG. 10 is a schematic drawing depicting a light-emitting device.
  • One aspect of the invention relates to a method for depositing material onto a substrate.
  • Another aspect of the invention related to methods for depositing nanomaterial onto a substrate.
  • a method for depositing nanomaterial onto a substrate comprises applying a composition comprising nanomaterial to a surface of a tape, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate.
  • Known techniques can be used to transfer the layer comprising nanomaterial from the tape surface to the substrate. Examples include, but are not limited to, application of pressure, laser writing, laser ablation, thermal transfer, and other techniques identifiable by a person of ordinary skill in the relevant art.
  • a mask can be positioned on the substrate prior to contacting the surface of the tape comprising nanomaterial to the substrate.
  • the nanomaterial can optionally be included in a composition.
  • the composition can further include a liquid or other carrier medium.
  • the composition can further include one or more additional components.
  • a nanomaterial typically includes nanoparticles having an average maximum dimension smaller than 100 nm.
  • nanoparticles include, for example, a semiconductor nanocrystal, a nanotube (such as a single walled or multi-walled carbon nanotube), a na ⁇ owire, a nanorod, a dendrimer, organic nanocrystal, organic small molecule, other nano-scale or micro-scale material or mixtures thereof.
  • Nanomaterial particles can have various shapes, including, but not limited to, sphere, rod, disk, other shapes, and mixtures of various shaped particles.
  • organic nanocrystals include, without limitation, J-aggregates, H-aggregates, and organic nanocrystals including aggregates with other dipole arrangements.
  • organic nanocrystals are described in S. Kirstein et al., "Herringbone Structures In Two- Dimensional Single Crystals of Cyanine Dyes. I. Detailed Structure Analysis Using Electron Diffraction", J. Chem. Phys. 103(2) July 1995, pages 816 et seq.; S. Kirstein et al., "Herringbone Structures In Two- Dimensional Single Crystals of Cyanine Dyes. II. Optical Properties", J. Chem. Phys. 103(2) July 1995, pages 826 et seq.; A.
  • the present invention is useful for depositing nanomaterials, including, but not limited to, nanomaterials with optical and/or electronic characteristics, in patterned or unpatterned arrangements.
  • a nanomaterial can include one nanomaterial or a mixture of two or more different nanomaterials.
  • Nanomaterials can be different based on, e.g. chemical composition, particle morphology (e.g., size, shape, surface area, particle size distribution, Full Width at Half-Maximum (FWHM), etc.), surface treatment(s) (e.g., not surface-modified, surface modified, and if surface modified, the details of the surface modification (e.g., composition, etc.)), particle structure (e.g., uncoated or coated; and if coated, the details of the coating, e.g., composition, thickness, nature of the coating (e.g., continuous, non-continuous, particulate, film, etc.)), performance characteristics (e.g., absorption properties, emission characteristics, etc.) of each nanomaterial, different combinations of chemical, physical, and/or performance aspects, etc.
  • surface treatment(s) e.g., not surface-modified, surface modified, and if surface modified, the details of
  • nanomaterial includes semiconductor nanocrystals.
  • Semiconductor nanocrystals comprise nanometer— scale inorganic semiconductor particles.
  • Semiconductor nanocrystals preferably have an average nanocrystal diameter less than about ISO Angstroms (A), and most preferably in the range of 12-150 A.
  • inorganic semiconductor nanocrystals comprise Group IV elements, Group II-VI compounds, Group H-V compounds, Group III-VI compounds, Group III-V compounds, Group IV-VI compounds, Group I-III-VI compounds, Group II-IV-VI compounds, or Group H-IV-V compounds, alloys thereof and/or mixtures thereof, including ternary and quaternary alloys and/or mixtures.
  • Examples include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, GaSe, InN, InP, InAs, InSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, Si, Ge, alloys thereof and/or mixtures thereof, including ternary and quaternary alloys and/or mixtures.
  • semiconductor nanocrystals preferably include a "core" of one or more first semiconductor materials, which may be surrounded by an overcoating or "shell” of a second semiconductor material.
  • a semiconductor nanocrystal core surrounded by a semiconductor shell is also referred to as a "core/shell” semiconductor nanocrystal.
  • the semiconductor nanocrystal can include a core having the formula MX, where M is cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, thallium, or mixtures thereof, and X is oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, or mixtures thereof.
  • Examples of materials suitable for use as semiconductor nanocrystal cores include, but are not limited to, CdS, CdO, CdSe, CdTe, ZnS, ZnO, ZnSe, ZnTe, MgTe, GaAs, GaP, GaSb, GaN, HgS, HgO, HgSe, HgTe, InAs, InP, InSb, InN, AlAs, AlP, AlSb, AIS, PbS, PbO, PbSe, Ge, Si, alloys thereof, and/or mixtures thereof, including ternary and quaternary alloys and/or mixtures.
  • Examples of materials suitable for use as semiconductor nanocrystal shells include, but are not limited to, CdS, CdO, CdSe, CdTe, ZnS, ZnO, ZnSe, ZnTe, MgTe, GaAs, GaP, GaSb, GaN, HgS, HgO, HgSe, HgTe, InAs, InP, InSb, InN, AlAs, AIP, AlSb, AIS, PbS, PbO, PbSe, Ge, Si, alloys thereof, and/or mixtures thereof, including ternary and quaternary alloys and/or mixtures. Other non-limiting examples are provided above.
  • the surrounding "shell” material can have a bandgap greater than the bandgap of the core material.
  • the shell can be chosen so as to have an atomic spacing close to that of the "core" substrate.
  • the surrounding shell material can have a bandgap less than the bandgap of the core material.
  • the shell and core materials can have the same crystal structure. Examples of semiconductor nanocrystals (core)shell structures include, without limitation: (CdSe)ZnS (core)shell, (CdZnSe)CdZnS (core)shell, and (CdS)CdZnS (core)shell.
  • the semiconductor nanocrystals are preferably members of a population of semiconductor nanocrystals having a narrow size distribution. More preferably, the semiconductor nanocrystals comprise a monodisperse or substantially monodisperse population of semiconductor nanocrystals. The monodisperse distribution of diameters can also be referred to as a size. In certain embodiments, the monodisperse population of semiconductor nanocrystals exhibits less than a 15% rms deviation in diameter of the nanocrystals, preferably less than 10%, more preferably less than 5%.
  • Methods of preparing monodisperse semiconductor nanocrystals include pyrolysis of organometallic reagents, such as dimethyl cadmium, injected into a hot, coordinating solvent. This permits discrete nucleation and results in the controlled growth of macroscopic quantities of nanocrystals. Preparation and manipulation of semiconductor nanocrystals are described, for example, in U.S. Patent 6,322,901 and 6,576,291, and U.S. Patent Application No. 60/550,314, each of which is hereby incorporated herein by reference in its entirety. Additional examples of methods of preparing semiconductor nanocrystal are described in U.S. Patent Application No.
  • One method of manufacturing a nanocrystal comprises a colloidal growth process. Colloidal growth occurs by rapidly injecting an M donor and an X donor into a hot coordinating solvent. The injection produces a nucleus that can be grown in a controlled manner to form a nanocrystal. The reaction mixture can be gently heated to grow and anneal the nanocrystal. Both the average size and the size distribution of the nanocrystals in a sample are dependent on the growth temperature. The growth temperature necessary to maintain steady growth increases with increasing average crystal size.
  • the nanocrystal is a member of a population of nanocrystals. As a result of the discrete nucleation and controlled growth, the population of nanocrystals obtained has a narrow, monodisperse distribution of diameters.
  • the monodisperse distribution of diameters can also be referred to as a size.
  • the process of controlled growth and annealing of the nanocrystals in the coordinating solvent that follows nucleation can also result in uniform surface derivatization and regular core structures. As the size distribution sharpens, the temperature can be raised to maintain steady growth. By adding more M donor or X donor, the growth period can be shortened.
  • the M donor can be an inorganic compound, an organometallic compound, or elemental metal.
  • M is cadmium, zinc, magnesium, mercury, aluminum, gallium, indium or thallium.
  • the X donor is a compound capable of reacting with the M donor to form a material with the general formula MX.
  • the X donor is a chalcogenide donor or a pnictide donor, such as a phosphine chalcogenide, a bis(silyl) chalcogenide, dioxygen, an ammonium salt, or a tris(silyl) pnictide.
  • Suitable X donors include dioxygen, bis(trimethylsilyl) selenide ((TMS) 2 Se), trialkyl phosphine selenides such as (tri-n-octylphosphine) selenide (TOPSe) or (tri-n-butylphosphine) selenide (TBPSe), trialkyl phosphine tellurides such as (tri-n-octylphosphine) telluride (TOPTe) or hexapropylphosphorustriamide telluride (HPPTTe), bis(trimethylsilyl)telluride ((TMS) 2 Te); bis(trimethylsilyl)sulf ⁇ de ((TMS) 2 S), a trialkyl phosphine sulfide such as (tri-n-octylphosphine) sulfide (TOPS), an ammonium salt such as an ammonium halide (e.g., NH 4 Cl), tris(tri
  • a coordinating solvent can help control the growth of the nanocrystal.
  • the coordinating solvent is a compound having a donor lone pair that, for example, has a lone electron pair available to coordinate to a surface of the growing nanocrystal.
  • Solvent coordination can stabilize the growing nanocrystal.
  • Typical coordinating solvents include alkyl phosphines, alkyl phosphine oxides, alkyl phosphonic acids, or alkyl phosphinic acids, however, other coordinating solvents, such as pyridines, furans, and amines may also be suitable for the nanocrystal production.
  • Suitable coordinating solvents include pyridine, tri-n-octyl phosphine (TOP), tri-n-octyl phosphine oxide (TOPO) and tris-hydroxylpropylphosphine (tHPP).
  • TOPO tri-n-octyl phosphine
  • TOPO tri-n-octyl phosphine oxide
  • tHPP tris-hydroxylpropylphosphine
  • TOPO tri-hydroxylpropylphosphine
  • a non-coordinating solvent can be used.
  • Size distribution during the growth stage of the reaction can be estimated by monitoring the absorption line widths of the particles. Modification of the reaction temperature in response to changes in the absorption spectrum of the particles allows the maintenance of a sharp particle size distribution during growth. Reactants can be added to the nucleation solution during crystal growth to grow larger crystals. By stopping growth at a particular nanocrystal average diameter and choosing the proper composition of the semiconducting material, the emission spectra of the nanocrystals can be tuned continuously over the wavelength range of 300 nm to 5 microns, or from 400 nm to 800 nm for CdSe and CdTe. The nanocrystal has a diameter of less than 150 A. A population of nanocrystals has average diameters in the range of 15 A to 125 A.
  • a semiconductor nanocrystal can have various shapes, including, but not limited to, sphere, rod, disk, other shapes, and mixtures of various shaped particles.
  • semiconductor nanocrystal can include a core/shell structure.
  • a semiconductor nanocrystal can include a core of a semiconductor material.
  • a semiconductor nanocrystal core can comprise, for example, and without limitation, a semiconductor material represented by the formula MX, where M is cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, thallium, or mixtures thereof, and X is oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, or mixtures thereof. Other examples are provided elsewhere herein.
  • the core includes a shell (also referred to as an overcoating) on a surface of the core.
  • the overcoat of a semiconductor material on a surface of the nanocrystal core can include for example, and without limitation, Group FV elements, Group II- VI compounds, Group H-V compounds, Group III-VI compounds, Group IH-V compounds, Group rV-VI compounds, Group I-III-VI compounds, Group H-FV-VI compounds, and Group H-IV-V compounds, for example, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, GaSe, InN, InP, InAs, InSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbS, PbS, P
  • ZnS, ZnSe or CdS overcoatings can be grown on CdSe or CdTe nanocrystals.
  • An overcoating process is described, for example, in U.S. Patent 6,322,901.
  • the overcoating can be between 1 and 10 monolayers thick.
  • the particle size distribution can be further refined by size selective precipitation with a poor solvent for the nanocrystals, such as methanol/butanol as described in U.S. Patent 6,322,901.
  • nanocrystals can be dispersed in a solution of 10% butanol in hexane. Methanol can be added dropwise to this stirring solution until opalescence persists. Separation of supernatant and flocculate by centrifugation produces a precipitate enriched with the largest crystallites in the sample. This procedure can be repeated until no further sharpening of the optical absorption spectrum is noted. Size-selective precipitation can be carried out in a variety of solvent/nonsolvent pairs, including pyridine/hexane and chloroform/methanol. The size-selected nanocrystal population can have no more than a 15% rms deviation from mean diameter, preferably 10% rms deviation or less, and more preferably 5% rms deviation or less.
  • semiconductor nanocrystals are optionally surface modified, including, but not limited to, for example, having one or more ligand groups attached thereto.
  • the ligands are derived from the coordinating solvent used during the growth process.
  • the surface can be modified by repeated exposure to an excess of a competing coordinating group to form an overlayer.
  • a dispersion of the capped semiconductor nanocrystal can be treated with a coordinating organic compound, such as pyridine, to produce crystallites which disperse readily in pyridine, methanol, and aromatics but no longer disperse in aliphatic solvents.
  • a surface exchange process can be carried out with any compound capable of coordinating to or bonding with the outer surface of the semiconductor nanocrystal, including, for example, phosphines, thiols, amines and phosphates.
  • the semiconductor nanocrystal can be exposed to short chain polymers which exhibit an affinity for the surface and which terminate in a moiety having an affinity for a suspension or dispersion medium. Such affinity improves the stability of the suspension and discourages flocculation of the semiconductor nanocrystal.
  • Nanocrystal outer layers are described in U.S. Patent 6,251,303, which is incorporated by reference in its entirety.
  • the coordinating ligand can have the formula:
  • k is 2, 3 or 5, and n is 1, 2, 3, 4 or 5 such that k-n is not less than zero;
  • each of Y and L independently, is aryl, heteroaryl, or a straight or branched C 2 - H hydrocarbon chain optionally containing at least one double bond, at least one triple bond, or at least one double bond and one triple bond.
  • the hydrocarbon chain can be optionally substituted with one or more C M alkyl, C 2 . 4 alkenyl, C 2 .
  • R a and R b independently, is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxylalkyl, hydroxyl, or haloalkyl.
  • An aryl group is a substituted or unsubstituted cyclic aromatic group.
  • a heteroaryl group is an aryl group with one or more heteroatoms in the ring, for instance furyl, pyiridyl, pyrrolyl, phenanthryl.
  • a suitable coordinating ligand can be purchased commercially or prepared by ordinary synthetic organic techniques, for example, as described in J. March, Advanced Organic Chemistry, which is incorporated herein by reference in its entirety. See also U.S. Patent Application No. 10/641,292 entitled “Stabilized Semiconductor Nanocrystals", filed 15 August 2003, which is hereby incorporated herein by reference in its entirety. See also other patents and patent applications referenced herein for additional descriptions of preparation methods.
  • TEM Transmission electron microscopy
  • Powder X-ray diffraction (XRD) patterns can provide the most complete information regarding the type and quality of the crystal structure of the nanocrystals.
  • Estimates of size are also possible since particle diameter is inversely related, via the X-ray coherence length, to the peak width.
  • the diameter of the nanocrystal can be measured directly by transmission electron microscopy or estimated from X-ray diffraction data using, for example, the Scherrer equation. It also can be estimated from the UV/Vis absorption spectrum.
  • a composition can include nanomaterial and a carrier medium (e.g., liquid, polymer, monomer, polymer or monomer solution, etc.).
  • a carrier medium can be one in which the nanomaterial does not dissolve or does not appreciably dissolve (e.g., solubility is less than 0.001 mg/ml).
  • the carrier medium can be one in which the ligand not soluble or not appreciably soluble.
  • the medium can be one in which the ligand is at least partially soluble.
  • Examples of a liquid component for inclusion in compositions including nanomaterial include, without limitation, those listed in the following Table 1, and mixtures of two or more thereof. Examples of mixtures include hexane and octane; benzene and xylene; tetrahydrofurane and anisole; etc.
  • liquids or mixtures of liquids can be used.
  • volatile liquids or mixtures of volatile liquids can be used.
  • a composition including nanomaterial and a liquid has a viscosity in a range of from about 0.1 centipoise (e.g., that of diethyl ether, methanol) to greater than 1500 centipoise (e.g., that of oils, glycerol).
  • a composition including a nanomaterial and liquid may also be referred to as an ink.
  • a preferred liquid comprises an organic non-polar solvent. More preferably, such carrier has a viscosity less than or equal to about 1 cP and also relatively high volatility.
  • other components can be included in the composition.
  • other components that can be optionally included in the composition include, but are not limited to, e.g., surfactants, solvents, co-solvents, buffers, biocides, viscosity modifiers, complexing agents, chelating agents, stabilizing agents (e.g., to inhibit agglomeration of the nanomaterial), humectants etc.
  • Other possible components include other additives of the type that may be included in ink or inkjet ink compositions.
  • Stabilizing agents can include, e.g., chemically attached functional groups or ligands to form a coating around individual nanoparticles.
  • the amount (e.g., concentration (wt/vol)) of nanomaterial included in a composition can be selected based upon the particular nanomaterial and desired attributes of the deposited nanomaterial (e.g., thickness, optical density, features of the deposited nanomaterial (e.g., patterned or unpattemed, sizes of the features of a pattern, etc.)). The amount can be readily determined by a person of ordinary skill in the art.
  • the composition includes at least about 0.1 mg/ml semiconductor nanocrystals and/or composition.
  • the composition can include at least 1 mg/ml, at least 5 mg/ml, at least 10 mg/ml, at least 25 mg/ml; at least 50 mg/ml, etc.
  • the nanomaterial and any other optional solid components are dispersed in the composition when introduced onto the transfer surface.
  • the dispersion is colloidal.
  • a composition useful for depositing nanomateriai onto a substrate includes nanomaterial.
  • the composition can further include a carrier medium (e.g., liquid, polymer, monomer, polymer or monomer solution, etc.).
  • the composition can further include one or more additional components.
  • nanomaterial comprises nanoparticles. Examples of nanoparticles include, for example, a semiconductor nanocrystal, a nanotube (such as a single walled or multi-walled carbon nanotube), a nanowire, a nanorod, a dendrimer, organic nanocrystal, organic small molecule, other nano-scale or micro-scale material or mixtures thereof.
  • Methods in accordance with the invention allow deposition of one or more nanomaterials and/or one or more compositions including nanomaterial onto a substrate.
  • Such nanomaterial(s) and/or composition(s) can be deposited onto the substrate in a patterned or unpattemed arrangement.
  • Methods in accordance with the invention are particularly useful for applying one or more nanomaterials to a predefined region of a substrate, which may optionally include other materials, layers, components, and/or structures disposed thereon.
  • nanomaterial can also be deposited with additional components included in a composition.
  • the predefined region is a region on the substrate where the nanomaterial can be selectively applied.
  • the nanomaterial and surface can be chosen such that the nanomaterial remains substantially entirely within the predetermined area.
  • Nanomaterial can be deposited onto the substrate such that the nanomaterial forms an unpattemed layer comprising nanomaterial within the predetermined area or a pattern comprising nanomaterial within the predetermined area.
  • the pattern can be a regular pattern (such as an array, or a series of lines), or an irregular pattern.
  • the substrate can have a region including the nanomaterial (the predefined region) and a region substantially free of nanomaterial.
  • the one or more nanomaterials are deposited onto the substrate at a thickness of about a monolayer. In some circumstances, the thickness can be greater than a monolayer.
  • the predefined region can be a discontinuous region. In other words, when the one or more nanomaterials are deposited onto the predefined region of the substrate, locations including nanomaterial can be separated by other locations that are substantially free of nanomaterial.
  • nanomaterial When deposited in a patterned arrangement, nanomaterial can be deposited in a pattern comprising features having at least one dimension at a micron-scale (e.g., less than 1 mm, less than
  • Nanomaterial can also be deposited in a patterned arrangement comprising features at greater than micron-scale.
  • a pattern comprising deposited nanomaterial having features on the micron scale may also be referred to herein as a micropattern.
  • a micropattern including 10-20 ⁇ m size features can be useful in light emitting device applications including, e.g., semiconductor nanocrystals.
  • the surface on which the nanomaterial can be deposited can have dimensions of 1 cm or greater, 10 cm or greater, 100 cm or greater, or 1,000 cm or greater.
  • Methods in accordance with the invention are scalable and can be useful in depositing a pattern comprising one or more nanomaterials over a wide range of surface areas.
  • the method is useful for depositing nanomaterial over very small areas (for example, 100 ⁇ m catheters) to very large areas, (for example, 12" square areas).
  • the method is also useful for depositing nanomaterial over surfaces with dimensions such as GEN2 (360 mm X 465 mm), GEN3 (550 mm X 650 mm), GEN3.5 (600 mm X 720 mm), GEN4 (730 mm X 920 mm), GEN5 ( 1110 mm X 1250 mm), GEN6 (1500 mm X 1800 mm), GEN7 (1900 mm X 2100 mm), and subsequent generations of glass that can be used, e.g., in displays.
  • areas onto which nanomaterial is applied can then be stitched (or tiled) together, to expand the printable area from 12" squares, to 'n x 12" squares' as is frequently done in the semiconductor lithography field.
  • a method for depositing nanomaterial onto a substrate comprises applying a composition comprising nanomaterial to a surface of a tape, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate.
  • a composition can further include liquid or another carrier medium.
  • a composition can further include other components.
  • the nanomaterial applied to a surface of the tape can be patterned or unpatterned.
  • a pattern can comprise an array of individual features at least one of which comprises nanomaterial. Typically, the individual features are spaced apart from each other. In certain embodiments, however, the features could be in contact with each other or even overlap.
  • a method for depositing nanomaterial onto a substrate comprises applying a composition comprising nanomaterial to a surface of a tape from a transfer surface, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate.
  • the nanomaterial applied to the substrate can be patterned or unpatterned
  • nanomaterial deposited by a method in accordance with the invention can include one or more nanomaterials, including, e.g., a mixture of two or more different nanomaterials.
  • nanomaterial is included in a composition, and two or more nanomaterials are to be deposited, different compositions including one or more different nanomaterials can be used.
  • the method can include applying different nanomaterials and/or mixtures of nanomaterials to a surface of a tape from a transfer surface in a single deposition step.
  • the method can include applying different compositions including different nanomaterials and/or mixtures of nanomaterials to a surface of a tape from a transfer surface in a single deposition step.
  • the method can include applying different nanomaterials and/or mixtures of nanomaterials to a surface of a tape from separate transfer surfaces in more than one deposition step. In another example, the method can include applying different compositions including different nanomaterials and/or mixtures of nanomaterials to a surface of a tape from separate transfer surfaces in more than one deposition step.
  • a composition includes liquid
  • all or substantially all of the liquid can be removed from the composition after the composition is applied to the tape.
  • This allows the nanomaterial and any optional non-liquid components of a composition to be deposited onto the substrate by a dry (e.g., liquid-free or substantially liquid-free) transfer.
  • a method including a dry transfer of nanomaterials onto the substrate can be advantageous when a liquid included in a composition can dissolve or otherwise react with the substrate.
  • a dry transfer process is preferred, for example, when transferring a composition including semiconductor nanocrystals from tape to an organic layer of a light-emitting device structure during device fabrication.
  • the composition can be deposited onto the substrate without prior removal the liquid therefrom.
  • the liquid can be removed after deposition of the composition(s) onto the substrate.
  • the time between application of composition(s) to the tape surface and deposition thereof onto the substrate is controlled to allow the deposition to occur while the composition(s) includes at least an amount of liquid.
  • a method of depositing one or more nanomaterials onto a substrate includes applying one or more liquid-free or substantially liquid-free nanomaterials to tape from a transfer surface; and depositing at least a portion of the nanomaterials from the tape onto the substrate.
  • This aspect of the invention can be particularly advantageous when depositing one or more nanomaterials onto a substrate in a predetermined pattern.
  • a transfer of nanomaterial(s) from the transfer surface to the tape in the absence of a liquid component blurring or distortion of patterned nanomaterial on the tape surface can be reduced.
  • Such blurring or distortion can occur, for example, when the liquid including nanomaterial spreads on or wets the tape surface.
  • a transfer surface can be planar or contoured.
  • a transfer surface can be rigid or flexible.
  • a transfer surface can be featureless or smooth (e.g. without elevations and/or depressions (e.g., grooves, recessed wells, etc.).
  • a smooth transfer surface can be useful, for example, in a method for depositing an unpatterned layer onto a substrate. Examples of other embodiments including a smooth transfer surface are described below.
  • a transfer surface can include one or more features (e.g., elevations and/or depressions (e.g., grooves, recessed wells, other three-dimensional features, etc.)). The arrangement of features can correspond to a predetermined pattern to be deposited onto a substrate.
  • a transfer surface including one or more depressions can be useful, for example, in a method for depositing a pattern comprising one or more nanomaterials onto a substrate.
  • a transfer surface including elevated features can also be useful for depositing a pattern onto a substrate.
  • a composition including nanomaterial disposed on the elevated features of the transfer surface can be picked up with tape in the predetermined pattern and deposited onto the substrate.
  • a transfer surface can include a planar surface.
  • a transfer surface can include a non-planar surface.
  • a transfer surface can be curved.
  • transfer surfaces include, without limitation, a plate including a flat section of material (metallic, polymeric, silicon, for example), that can be smooth or include one or more depressions (e.g., a flat cliche) , a roller (e.g., with a circular, elliptical, or other rounded cross- section) including a predetermined pattern, a roller shaped transfer surface with a smooth surface (e.g., a roller shaped clich ⁇ ), etc.
  • a plate including a flat section of material metallic, polymeric, silicon, for example
  • a roller e.g., with a circular, elliptical, or other rounded cross- section
  • a roller shaped transfer surface with a smooth surface e.g., a roller shaped clich ⁇
  • transfer surface useful in the present invention is known in the art as a cliche. Other types of transfer surfaces can also be readily identified and used.
  • a rigid transfer surface is preferred.
  • the transfer surface is made of polymer lined steel, thin ( ⁇ 1 mm) steel sheet or thick ( ⁇ 10 mm) steel plate.
  • Other materials that can be used to fabricate a transfer surface include metal (e.g., aluminum, etc.) metal alloys, silicon, glass, ceramic, etc.
  • the transfer surface is fabricated from steel plate.
  • the shape of the grooves can be rectangular or another geometric shape such as lines, square, triangular, circular, semi-circular, elliptical, semi-elliptical, other geometrical shapes, irregular shapes, customized shapes, etc.
  • the grooves can have the same shape or may include any number of different combinations of geometrical, irregular, customized, etc. shapes, for example.
  • the dimensions of a groove can optionally be on a micron scale (e.g., less than 1 mm, less than 500 ⁇ m, less than 200 ⁇ m, less than 100 ⁇ m, less than 50 ⁇ m, or 20 ⁇ m, 10 ⁇ m or less), or on a millimeter-scale or on a centimeter-scale or larger. Larger or smaller dimension grooves can also be used, depending on the predetermined pattern to be applied to substrate.
  • a micron scale e.g., less than 1 mm, less than 500 ⁇ m, less than 200 ⁇ m, less than 100 ⁇ m, less than 50 ⁇ m, or 20 ⁇ m, 10 ⁇ m or less
  • Larger or smaller dimension grooves can also be used, depending on the predetermined pattern to be applied to substrate.
  • the depth of a groove may be 0.01 ⁇ m (10 nm) to 100 ⁇ m, but is typically 25 ⁇ m in depth.
  • the grooves can be arranged in a pattern.
  • a transfer surface including depressions (e.g., grooves, recessed wells, other three-dimensional features etc.) arranged in a pattern
  • the size, shape, and arrangement of the patterned depressions in a transfer surface can be designed so as to correspond to a predetermined pattern to be deposited onto the substrate.
  • the depth and contour of the depressions in the transfer surface are also designed to produce the predetermined pattern to be deposited onto the substrate.
  • a transfer surface including a predetermined pattern of elevations or depressions (e.g., grooves, recessed wells, other three-dimensional features etc.) will permit the transfer of a predetermined pattern from the transfer surface to a surface of a tape.
  • a pattern can be formed on a transfer surface by, for example, etching, general photolithography, or other known techniques in the relevant art.
  • FIG. 1 A illustrates a plan view of an example of a clich ⁇ 100. As shown, a pattern of rectangular shaped grooves 102 is formed in the surface 104 of the cliche. Although the figure depicts rectangular shaped grooves, as discussed above, the shape, size, arrangement, depth, and contour of the grooves are selected based on the predetermined pattern to be deposited onto the substrate.
  • FIG. 1 B illustrates a plan view of another example of a cliche 100.
  • the pattern of line-shaped grooves 102 is formed in the surface 104 of the cliche.
  • the cliche includes a pattern of lines with different widths and different spacings.
  • fewer or more different compositions can be included in the grooves.
  • a transfer surface includes a pattern of grooves, nanomaterial, and/or a composition including nanomaterial, can be introduced into one or more grooves in accordance with depositing the predetermined pattern including nanomaterial onto a substrate.
  • the one or more nanomaterials or compositions can be included in at least a portion of a groove in accordance with the individual features of the predetermined pattern to be deposited on a substrate.
  • the nanomaterial and/or composition included in the various grooves can be the same or different.
  • the predetermined pattern including the composition(s) and/or nanomaterial(s) included in the grooves of the transfer surface, as the case may be, preferably becomes reversibly adhered to the tape surface.
  • the predetermined patterned can thereafter deposited onto the substrate by contacting the nanomaterial disposed on the tape surface thereto.
  • a predetermined pattern can be deposited onto the substrate by including elevated features, corresponding to the predetermined pattern, on all or a portion of the transfer surface.
  • the nanomaterial disposed on the elevated features of the transfer surface can be picked up with a surface of a tape in the predetermined pattern and deposited onto the substrate by contacting the tape thereto.
  • nanomaterial disposed on the transfer surface can be selectively removed in a predetermined pattern to be deposited onto the substrate.
  • the transfer surface can be smooth or unpatterned.
  • one or more nanomaterials and/or one or more compositions comprising nanomaterial can be applied to the smooth transfer surface and applied to a tape surface as an unpatterned layer.
  • a pattern comprising one or more compositions or nanomaterials can be formed on the unpatterned transfer surface by, e.g., inkjet printing, silk- screening, other screen-printing technique, or other known technique for creating a pattern comprising one or more compositions or nanomaterials on the smooth transfer surface.
  • a pattern formed on a transfer surface in such manner corresponds to the predetermined pattern including one or more nanomaterials to be deposited onto the substrate.
  • a predetermined pattern can be formed on a transfer surface with use of a mask including one or more apertures. The number, size, shape, and arrangement of the apertures will be selected based on the predetermined pattern that is desired.
  • a mask including one or more apertures corresponding to the predetermined pattern can be placed on the transfer surface before the nanomaterial and/or composition is to be picked up by a surface of a tape.
  • the tape surface preferably unfeatured, can pick up the nanomaterial and/or composition including nanomaterial from the transfer surface through the apertures arranged in a predetermined pattern to form patterned nanomaterial and/or composition thereon.
  • the tape surface including the patterned nanomaterial and/or composition can thereafter be contacted to the substrate to deposit the pattern thereon.
  • the nanomaterial and/or composition is preferably introduced to the transfer surface prior to positioning the mask thereon. In certain embodiments, any liquid is preferably removed from the nanomaterial and/or composition prior to positioning of the mask on the transfer surface.
  • nanomaterial and/or a composition including nanomaterial is deposited onto the transfer surface through a mask including one or more apertures arranged in the predetermined pattern. After the mask is removed, the patterned nanomaterial deposited onto transfer surface through the apertures can be picked up by a surface of a tape, preferably with an unfeatured surface. The nanomaterial can thereafter be deposited onto the substrate from the tape surface.
  • a predetermined pattern can be formed on a substrate by positioning a mask including one or more apertures arranged in a desired predetermined pattern on the substrate prior to contacting the tape surface including nanomaterial to the substrate.
  • a pattern of the nanomaterial and/or composition is applied to the substrate.
  • the nanomaterial and/or composition on the tape surface is preferably dry (e.g., at least substantially free of liquid) prior contacting the tape surface to the substrate through the mask apertures.
  • nanomaterial may be deposited through less than all of the apertures.
  • the nanomaterial and/or composition on the tape surface preferably comprises an unpatterned layer.
  • the deposition (also referred to herein as printing) step(s) are preferably carried out in a nitrogen or vacuum environment.
  • a mask can be fabricated from a class of films comprising polyimides including fluorinated polyimide films or film coated, at least on one side, with a fluorinated material.
  • a film coated, on at least one side, with a coating comprising an aromatic material can be coated with one side of the film and the other side can be coated with an aromatic material.
  • a fluorinated polyimide film or film coated at least on one side, with a fluorinated material, with the side of the film including the fluorinated material being positioned against the substrate.
  • a mask comprises plastic and/or a plastic coating
  • it is preferably baked out at elevated temperature with vacuum to remove VOCs, etc. prior to printing.
  • a mask comprising a polyimide film having a thickness of 1 mil polyimide can be used. Thinner and/or thicker masks are also suitable. Masks thinner than O.S mil are desirable for printing higher resolution patterns. Masks with a thickness less than 0.5 mil may require tensioning. Alternatively, the rigidity and/or dimensional stability of masks with a thickness less than O.S mil can be enforce with a thin steel foil. In certain other embodiments, a mask can comprise a rigid foil which optionally can be coated on one or both sides with a soft coating (e.g, Teflon).
  • a soft coating e.g, Teflon
  • a mask can be patterned with a predetermined pattern by known techniques (including, but not limited to, photo-etching and laser patterning) or unpatterned.
  • film materials from which a mask can be made include, without limitation, polyimide films such as, for example, and without limitation, 6FDA-ODA Fluorinated Polyimide, 6FDA-PMDA Fluorinated Co-Polyimide, 6FXDA-6FDA Fluorinated Polyimide Foam, Amoco Ultradel 4212 HFDA-APBP Polyimide, Au/Cr/Polyimide Composite, BPDA-ODA Polyimide, BPDA-PDA Polyimide Film, BPDA-PFMB Polyimide, BTDA-APB Polyimide, BTDA-ODA Polyimide, BTDA-PDA Polyimide, Ciba-Geigy Probimide 348 PMDA-ODA Polyimide, Ciba- Geigy Probimide 412 PSPI, Ciba-Geigy Probimide 414 PSPI, Ciba-Geigy XU-287 Soluble
  • a mask can further include a hole in each of the four corners to mount and tension a mask to a rigid frame, which is preferred with thin masks, as discussed above.
  • Various known techniques can be used to align a series of masks to be used to print and register multiple nanomaterials on a single substrate.
  • the mask can be placed against the transfer surface or substrate without gaps in between the transfer surface or substrate, as the case may be, and the underside of the mask.
  • One or more nanomaterials or compositions can be transferred from the transfer surface to tape surface by, for example, contacting (e.g., pressing) the tape surface against the transfer surface including the one or more compositions or nanomaterials to be deposited.
  • the one or more compositions or nanomaterials transferred to the tape surface from the transfer surface preferably become reversibly adhered to the tape surface for later deposition onto the substrate.
  • the one or more compositions can thereafter be deposited from the tape surface onto the substrate. If a wet transfer of composition(s) onto the substrate is desired, the time between patterning the tape surface and depositing the pattern onto the substrate is minimized to allow the pattern to transfer while the patterned nanomaterial still includes at least an amount of the liquid.
  • the liquid can be removed from composition(s) by, for example, evaporation, before the remainder of the composition (e.g., nanomaterial and any other optional components) is deposited on the substrate.
  • a dual dry transfer includes a liquid- free or substantially liquid-free transfer of one or more nanomaterials from the transfer surface to the tape surface and a liquid-free or substantially liquid-free transfer or the one or more nanomaterials from the tape surface onto the substrate.
  • a substantially liquid-free transfer includes, for example, no more than about 10 parts per hundred liquid, preferably no more than about 10 parts per thousand liquid, and more preferably no more than about 10 parts per million liquid.
  • one or more nanomaterials when one or more nanomaterials are introduced to a transfer surface as a component of a composition that also includes liquid, one or more nanomaterials can be transferred from the transfer surface to a tape surface by, for example, contacting the tape surface against the transfer surface after the liquid is removed from the composition.
  • the liquid can be removed, for example, by evaporation at ambient conditions, by application or heat to accelerate evaporation, by adjusting the pressure to accelerate evaporation, by modifying the temperature and pressure to accelerate evaporation, etc.
  • the one or more nanomaterials transferred to a tape surface from the transfer surface preferably become reversibly adhered to the tape surface upon contacting the tape surface to the transfer surface.
  • the one or more nanomaterials can thereafter be deposited from the tape surface onto the substrate.
  • a dry transfer process of one or more materials from the tape surface onto the substrate can be advantageous when the liquid of the composition(s) including the nanomaterial(s) can dissolve or otherwise react with the surface of the substrate.
  • Employing a dry transfer of nanomaterial(s) from the tape surface onto the substrate frees the substrate of solubility and surface chemistry requirements.
  • a dual dry transfer can also be used to deposit unpatterned layers comprising nanomaterial.
  • Methods in accordance with the invention can be used to deposit a pattern comprising two or more different nanomaterials onto a substrate. The two or more different nanomaterials can be deposited sequentially or in a single step.
  • each of the two or more different compositions or nanomaterials can be deposited in sequential separate depositions steps.
  • This embodiment can be used, for example, when depositing a pattern comprising different color compositions or nanomaterials, and each color is deposited onto the substrate separately.
  • each transfer is aligned and registered so that the predetermined pattern is deposited onto the substrate at a predefined location.
  • the method is compatible with various well-known alignment and registration techniques for example, when more than one pattern is deposited onto the substrate in more than one transfer.
  • Factors that can affect the registration of subsequent printing steps onto a single substrate include multiple well pattern (e.g., groove) offset, as well as the travel distance from one nanomaterial deposition to the next. Since both of these parameters can be tuned on the micron scale, high repeatability after tuning is expected.
  • two or more different compositions or nanomaterials are deposited by a single transfer step.
  • a transfer surface which includes the two or more different compositions or nanomaterials on the surface thereof.
  • the two or more nanomaterials can be included in the grooves of a single transfer surface for simultaneous transfer.
  • the two or more nanomaterials can by patterned on an smooth transfer surface by, e.g., inkjet or silk-screen printing, other screen-printing technique, vapor deposition (e.g., including masks to form a pattern comprising nanomaterials).
  • each composition or nanomaterial can be applied to the same tape surface one at a time in separate application steps to provide the predetermined arrangement of nanomaterials thereon.
  • the lateral offset of the patterns of the different nanomaterials, or compositions can be better-controlled than when each of the different nanomaterials or compositions are transferred separately. This can reduce or preferably eliminate variation from printing to printing. Expected registration accuracy and repeatability can be better than lOO ⁇ m, as good as l ⁇ m, and eventually as good as IOnm with precise mechanical systems.
  • the transfer surface can include a predetermined arrangement of different compositions that include semiconductor nanocrystals that emit light at different wavelengths. By including such arrangement of semiconductor nanocrystals that emit light at different wavelengths, a multicolor pattern can be formed on a tape surface for deposition onto the substrate.
  • Embodiments of the invention can also optionally include transferring more than one layer simultaneously, for example a blanket deposited (unpatterned) layer of a first material (e.g., metal, metal oxide, etc.) can be applied to a surface of a tape and a patterned second material (e.g., semiconductor nanocrystals, etc.) applied thereto. Upon contacting the tape surface to the substrate, the patterned second material is transferred as well as the blanket of first material.
  • a blanket deposited (unpatterned) layer of a first material e.g., metal, metal oxide, etc.
  • a patterned second material e.g., semiconductor nanocrystals, etc.
  • the nature of the substrate, and/or the end-uses for an article or device including the deposited composition or nanomaterial it may also be desirable to carry out the method in a controlled environment, e.g., in a hood, glove box, under an inert atmosphere, under nitrogen, etc.
  • the transfer surface can be treated (e.g., by application of one or more coatings) or otherwise surface modified (e.g., chemical modification of the surface, energetic treatments (including, but not limited to, plasma treatment, laser treatment, etc.), or other suitable surface-modification techniques).
  • a surface treatment can be applied to all or one or more portions of the surface.
  • a surface treatment of the transfer surface can be included whether the surface is featureless or whether the surface includes features (e.g., one or more grooves).
  • a surface treatment can include different treatments to different areas of the transfer surface.
  • the grooves e.g., the side walls and trough of the grooves
  • the top transfer surface between the grooves
  • the treatments can be applied, for example, to alter the properties (e.g., wetting attributes) of the transfer surface or portions thereof.
  • properties e.g., wetting attributes
  • Such surface energy modifications can be made, for example, by including a coating on the surface of the grooves of the transfer surface, on the non- grooved portion of the transfer surface, or both.
  • a first coating is applied to the surface of the grooves and a second coating is applied to the rest of the transfer surface, each coating material having either hydrophilic or hydrophobic properties, selected to reduce spreading.
  • various surface treatments that can be applied to the transfer surface include trichlorosilanes, other silylation treatments, teflon, etc. Selection of other surface treatments can be readily made by those of ordinary skill in the relevant art. In certain embodiments, silanized transfer surfaces can be preferred.
  • the surface energy of the groove surface can be modified to enhance wettability of the groove surface so that the composition dispensed in the groove spreads within the groove.
  • the surface energy of the non-grooved surface of the transfer surface is modified to decrease the wettability so that the spreading of the composition on the non-grooved transfer surface is reduced, and preferably prevented.
  • Modification of the non-grooved transfer surface can reduce the transfer of pattern defects that can result from the spread or other occurrence ⁇ ) of composition or nanomaterial on the non-grooved transfer surface at or prior to transfer of the composition from the groove(s) to the tape.
  • Modification of the grooves can facilitate the spread of the composition within the entire groove to assist pick-up of the full groove shape and size.
  • a tape has a predetermined dimension so that a pattern can be formed by one time transfer, even, for example, in case of a display device having a large area by using an tape having dimensions corresponding to a selected area of the display device.
  • the tape preferably has a configuration and dimensions selected for picking up the pattern formed from the filled transfer surface grooves.
  • the tape can be configured to move or be moved relative to the position of other components of the printing system being used, e.g., the transfer surface and/or the uppermost surface of the substrate on which a nanomaterial or composition is to be applied.
  • the surface of the tape can include an elevation or a depression, or the tape can be substantially free of elevations and/or depressions.
  • the surface of a tape to which nanomaterial is to be applied can be smooth or featureless (e.g., an absence of elevations and/or depressions of a pattern). In certain other embodiments, it can be patterned (e.g., featured).
  • a surface chemistry layer can be disposed over the surface of a tape to which nanomaterial is to be applied.
  • a surface chemistry layer can be applied by physical vapor deposition (PVD), chemical vapor deposition (CVD) , or liquid or gas phase coating by a self- assembled monolayer, depending on the desired material surface properties.
  • the composition of the surface chemistry layer can be selected to readily adhere and release a composition including nanomaterial , in a wet transfer, or nanomaterial, in a dry transfer.
  • the surface chemistry layer can optionally act as an adhesion/surface chemistry layer for the composition or nanomaterial.
  • Aromatic organic polymers, deposited by chemical vapor deposition, can be used as a surface chemistry layer. See, for example, S. Coe-Sullivan, et al., Advanced Functional Materials, 15, 1 1 17-1 124 (2005), which is incorporated by reference in its entirety.
  • the surface chemistry layer can be chosen to compatible with spreading of the composition which includes nanomaterial and a liquid. For example, with a liquid comprising chloroform, the surface chemistry layer can be a chemical vapor deposited Parylene-C layer or other surface chemistry material.
  • a surface chemistry layer comprising Parylene-C can be included on a surface of tape to assist complete release of the nanomaterial from the surface thereof.
  • a surface chemistry layer comprising Parylene-C is compatible with a wide range of liquids (e.g., non-polar organic liquids). Parylene-C is an aromatic polymer that can form thin and conformal coatings exhibiting highly inert properties.
  • Parylene-C makes it a suitable surface chemistry layer for use in depositing nanomaterials comprising semiconductor nanocrystals, particularly when deposited in thin layers including same.
  • a surface chemistry layer can include different parylene compositions or other surface chemistry materials (e.g., but not limited to, surface modifying organic molecules, plastics, and other surface chemistry treatments known or identifiable by a skilled artisan in the relevant art for achieving the desired surface properties).
  • Other parylene materials that could be used in a surface chemistry layer include, for example, but are not limited to, Parylene, Parylene-N, Parylene-F, Parylene-D, Parylene-HT, Parylene AF4, etc.
  • other surface treatments e.g., energetic treatments including, but not limited to, plasma treatment, laser treatment, etc. known or recognized in the art can be used.
  • a surface chemistry layer comprising Parylene-C may undergo as least partial delamination from PDMS.
  • The can occur for example, due to temperature effects (in light of the differences between the thermal coefficients of the two materials) and/or upon repeated application of pressure.
  • Such delamination problems can be reduced or avoided with use of surface chemistry release layer comprising organic molecular compounds.
  • Such compounds can be included in a surface coating on a tape surface.
  • the surface coating has a surface energy less than about 50 mJ/m 2 , more preferably less than about 30 mJ/m 2 , and most preferably less than about 20 mJ/m 2 .
  • the organic molecular compounds can be aromatic molecular compounds.
  • the surface chemistry layer comprises xxx-silanes.
  • Such materials include functional groups that can bond with functional groups at the elastomer surface and self-align themselves on the surface forming an organized coating. It is expected that these materials will remain immune to the dimensional changes in the elastomer originating from temperature variations or mechanical impact, and would maintain its de-wetting function over extended period of time.
  • Examples of organic molecular compounds for inclusion in a surface chemistry release layer include, but are not limited to, aromatic organic molecular compounds.
  • compounds for inclusion in a surface chemistry release layer include, but are not limited to, ethyltrichlorosilane, ethyltriethoxysilane, n-propyltrichlorosilane, n- propyltrimethoxysilane, n-butyltrichlorosilane, n-butyltrimethoxysilane, n-hexyltrichlorosilane, n- hexyltrimethoxysilane, n-octyltrichlorosilane, n-octyltriethoxysilane, n-decyltrichlorosilane, n- dodecyltrichlorosilane, n-dodecyltriethoxysilane, n-octadecyltrichlorosilane, n- octadecyltriethoxysilane, n-
  • the tape surface is contacted to the surface of the substrate under conditions to cause at least a portion of the nanomaterial included on the tape to be deposited onto the substrate
  • the tape can be contacted to the substrate at a pressure of at least 0.1 lb/in 2 for at least a period of time effective for transferring at least a portion of the nanomaterial onto the substrate, e.g., thirty seconds or less.
  • the pressure is at least 1 lb/in 2 ', but less than 50 Ib/ in 2 .
  • the pressure is in the range from about 100 Ib/ in 2 to about 500 Ib/ in 2
  • the pressure is less than the pressure at which the film or substrate is damaged.
  • compositions including one or more nanomaterials can be delivered to a transfer surface by various techniques.
  • the composition(s) can be dispensed from an inkcup, a micro-dispenser (e.g., a needle, inkjet print head, nozzles, syringe, etc.), an array of micro-dispensers (e.g., an array of needles, an array of multiple inkjet heads, an array of nozzles, misters, and array or syringes, etc.) that are movably mounted to be positioned over and aligned with the location on the transfer surface to which one or more compositions are to be dispensed.
  • a predetermined metered amount of a composition is dispensed.
  • Techniques for delivering or dispensing composition to a transfer surface will be discussed further below.
  • various masking techniques can be further included with techniques for delivering or dispensing a compositions selectively to a transfer surface.
  • one or more compositions can be dispensed to one or more grooves of the transfer surface by various techniques, including, but not limited to, use of an inkcup or from a micro-dispenser or an array of micro-dispensers (e.g., needles, inkjet nozzles, misters, etc.) positioned over and aligned to dispense a metered amount of composition into each groove to be filled.
  • a micro-dispenser e.g., needles, inkjet nozzles, misters, etc.
  • An inkcup technique can be particularly useful for dispensing the composition into transfer surface grooves.
  • Any type of inkcup can be used, for example, an open inkcup, a closed inkcup, or a pressurized inkcup.
  • the content In an open inkcup, the content is confined in a well that is open to the atmosphere. Depending on the properties of the content, the content of an open inkcup can experience variations in concentration and viscosity caused by evaporation. Such variations can affect the quality of the pattern of nanomaterial that is deposited onto the substrate.
  • a closed inkcup In a closed inkcup, the content is confined in a well that is closed to the atmosphere, so variations to the content that can result from evaporation are reduced or eliminated. For this and other reasons, a closed inkcup is preferred.
  • a closed inkcup can be positioned upside down and slide over the transfer surface or the transfer surface may slide over the inking surface of the inkcup. The latter approach requires the inkcup to be pressurized.
  • a pressurized inkcup typically includes a diaphragm that supports the ink well and can be raised to wet the transfer surface pattern and then retracted.
  • the pressurized ink cup can be particularly useful when printing has to be done on the surfaces that are not horizontally positioned relative to the inking surface of the inkcup.
  • the composition to be dispensed is confined within the inkcup.
  • the edge of the inkcup that is in contact with the transfer surface during the dispensing of the composition is sometimes referred to as a doctor ring.
  • This edge in contact with the transfer surface forms a seal with the transfer surface.
  • the seal can be improved by application of pressure.
  • the seal between the inkcup edge and the transfer surface depends upon the flatness of these parts and also on surface finish of each.
  • the area of the transfer surface containing the grooved pattern is preferably planar and preferably smooth.
  • the sealing force between the ink-cup and surface of the transfer surface is also dependent on the mass of the inkcup and any additional pressure applied to the inkcup when contacted to the transfer surface.
  • the seal between the inkcup and surface of the transfer surface can be further reinforced by, for example, a magnetic force originated by magnets located within the body of the ink-cup and under transfer surface that is magnetic, e.g., a steel plate.
  • Inkcups can be used with compositions of having viscosities, for example, from greater than about 1 cP to about 20 cP, less than about 1 cP, greater than about 2OcP, etc.
  • the edge of the inkcup that is in contact with the transfer surface acts as a doctor blade.
  • the composition is filled into the grooves over which the inkcup is moved, and the composition which remains at the surface of the transfer surface between the grooves is removed.
  • Manipulation of pressure allows the control of leakage of low viscosity inks from the transfer surface/inkcup assembly, as well as control of concentration variations that could be associated with any such leakage.
  • compositions When two or more different compositions are to be dispensed into certain transfer surface grooves, they are preferably dispensed from an inkcup one composition at a time.
  • a tight seal is maintained between the portion of the inkcup (e.g., doctor ring) in contact with the transfer surface and the transfer surface itself to confine the composition within the cup.
  • the portion of the inkcup in contact with the transfer surface comprises a substantially smooth, planar finish.
  • the surface energy of the portion of the inkcup in contact with the transfer surface can be modified to increase the dewetting characteristics thereof with respect to the composition being dispensed by the inkcup.
  • Such modification of the inkcup can assist in reducing the possibility of leakage of the composition through any surface imperfections at the seal between the inkcup and the transfer surface so that the composition preferably remains confined within the cup when moving across the transfer surface until deposited in the grooves of the transfer surface pattern.
  • the surface modification of the inkcup edge can optionally be utilized with one or more surface energy modifications of the transfer surface(s) discussed above. It is believed that any such surface modifications, alone or in combination, can extend the range of liquid viscosity to lower values, and improve uniformity of transferred patterns.
  • the mating seal counterparts, the doctor ring, and transfer surface are free of surface defects such as cracks, grooves, indentions, or even micro scale damage to prevent leakage of the composition.
  • the edge of the inkcup in contact with the transfer surface and/or the non-grooved surface of the transfer surface are optionally planarized and/or polished to reduce, and preferably, eliminate defects that can result in leakage of composition from the mated surfaces while the composition is being dispensed into the grooves.
  • these two surfaces comprise materials with different hardnesses, such as, for example, a cliche comprising steel and an inkcup with an edge comprising a ceramic material that is softer than the steel used to fabricate the cliche.
  • a cliche comprising steel and an inkcup with an edge comprising a ceramic material that is softer than the steel used to fabricate the cliche.
  • Various other materials of construction and/or their combinations, such as various ceramics, ceramic coating, glass, metals, or silicon may alternatively be utilized, for the transfer surface and inkcup edge.
  • An inkcup can be used in a static fashion, where the cup is filled, sealed, and not tampered with through successive prints.
  • a flow system can optionally be utilized to reflow the composition from the inkcup to a reservoir, thereby maintaining and stabilizing the composition concentration and viscosity.
  • the composition in a reflow loop may further optionally be monitored for concentration (via various optical means, for example) and the concentration maintained actively by addition of controlled quantities of carrier medium or concentrated composition or nanomaterial into the reflow loop to lower or raise the concentration of nanomaterial in the composition.
  • Another technique that is particularly useful for dispensing one or more compositions (e.g., different colored compositions) onto a transfer surface includes use of a micro-dispenser or an array of micro-dispensers (e.g., needles, inkjet nozzles, etc.) positioned over and aligned to dispense such composition or compositions thereto.
  • the transfer surface includes one or more depressions (e.g., grooves, recessed wells, etc.), in which case, the micro-dispenser or array of micro-dispenses can be aligned to deliver the composition(s) into the individual grooves.
  • Such micro-dispensers can optionally deliver different compositions to the transfer surface simultaneously or sequentially.
  • the transfer surface grooves can be filled by moving the transfer surface relative to the micro-dispenser(s) or alternatively, the micro-dispenser(s) can be moved relative to the grooves of the transfer surface, with the moving component being stopped at intervals selected to permit filling of unfilled grooves until all of the grooves are Tilled.
  • a micro-dispenser can be used to fill each of the grooves with the same composition.
  • Two or more different compositions can be dispensed into the transfer surface grooves by sequential delivery of each composition from a micro-dispenser.
  • Two or more different compositions can be dispensed into the transfer surface grooves non-sequentially.
  • an array of multiple micro-dispensers e.g., an ink jet system having multiple print heads, can dispense different nanomaterials in a non-sequential manner.
  • An array of micro-dispensers can also be programmed to dispense compositions into the grooves sequentially or in accordance with another predetermined order based on the pattern, groove location, dimensions of the transfer surface, etc.
  • FIG. 3 depicts a schematic of an example of a system including an array of micro-dispensers for dispensing one or more compositions into grooves of a cliche:
  • the cliche 450 includes a predetermined pattern of grooves in the upper surface 455 thereof.
  • An array micro-dispensers 410 is disposed over the cliche to dispense compositions into the grooves. At dispensing time, each micro-dispenser is aligned with the groove into which a given composition is to be dispensed.
  • FIG. 4 depicts a schematic of example of a system for dispensing more than one composition into grooves of a cliche.
  • the system includes an array of micro-dispensers that are spatially arranged for dispensing compositions into the predetermined pattern formed by the array of grooves on the transfer surface.
  • micro-dispensers can be positioned along a dimension (e.g., length, width, diagonal, etc.) of the cliche.
  • the individual micro-dispensers of an array can be arranged in a linear arrangement, but the arrays are positioned above the transfer surface at an angle to allow dispensing compositions into closely spaced grooves.
  • a linear array of micro-dispensers are positioned above transfer surfaces that are disposed on an angle. Other configurations of the transfer surface grooves and the array of micro-dispensers are possible.
  • the relative placement of the micro-dispensers corresponds to the pattern of the clich ⁇ so that when a composition is dispensed into a groove, the dispensed composition will spread in or wet a groove of the cliche due to surface tension and gravity. Subsequent to filling a groove, the micro-dispenser can be moved to be positioned over the next groove to receive the same composition. The micro- dispenser array will continue to move over the area of the pattern dispensing the composition in a continuous mode or by multiple injections. A second micro-dispenser array will similarly dispense a second composition into the appropriate grooves in accordance with the predetermined pattern.
  • the predetermined pattern is transferred to a tape surface and the pattern can thereafter be applied to the substrate.
  • the one or more different compositions e.g., three different compositions, each respectively comprising, e.g., blue-emitting, green-emitting, and red-emitting semiconductor nanocrystals (also referred to as quantum dots (abbreviated as "QD" in FIG. 4)
  • QD quantum dots
  • one or more compositions or nanomaterials are deposited onto a substrate in a single deposition step.
  • This single transfer process reduces and preferably eliminates variations in the concentrations of nanomaterial in the composition during the deposition of the pattern to the substrate.
  • a single deposition step to transfer a complete pattern or multiple components of a pattern avoids the need to register subsequent stamps to the previously deposited patterns. Further, by reducing the number of instances of contact between the tape and the substrate to which nanomaterial has been previously applied, the possible damage to, or disruption of, the previously applied nanomaterial is reduced. For example, in depositing a pattern comprising different color nanomaterials comprising semiconductor nanocrystals to a substrate, a single step transfer reduces the risk of damage to the patterned nanomaterials. This can be particularly advantageous when the nanomaterials are applied in thicknesses of several monolayers or less.
  • multiple compositions can be dispensed from micro-dispensers disposed over the transfer surface in an array.
  • Each of the micro-dispensers can dispense a composition at the same or different times.
  • the transfer surface can be moved under a positioned dispenser or micro-dispenser array, the dispenser or micro-dispenser can be moved over a positioned transfer surface, or the transfer surface and array can each be moved into alignment at or prior to the time the grooves are filled.
  • To transfer a pattern comprising different nanomaterials in a single transfer step all of the various compositions including the different nanomaterials to be deposited are dispensed into the patterned grooves before the tape is contacted to the transfer surface.
  • a dry transfer for example, the transfer surface is not contacted to the substrate until any liquid component of the composition(s) evaporates from the transfer surface, leaving liquid-free, or substantially liquid-free, nanomaterials on the transfer surface.
  • a substantially liquid-free transfer includes, for example, no more than about 10 parts per hundred liquid, preferably no more than about 10 parts per thousand liquid, and more preferably no more than about 10 parts per million liquid.
  • the ability to transfer a pattern comprising more than one nanomaterial by a single transfer further avoids the need to register the alignment of successive transfers of separate transfers of each individual nanomaterial and eliminates the need to index successive transfers of each individual nanomaterial. Scaie-up can also be facilitated.
  • FIG. 5 depicts the relative arrangement of a tape and substrate to receive the deposited composition(s) or nanomaterial(s).
  • the tape is contacted to the substrate with use of a presser (depicted in the illustrated example as a stamp).
  • the presser comprises a roller with a circular cross-section.
  • a roller with an oval cross section, a stamp, or other device suitable for depressing the tape against the transfer surface and/or substrate may optionally be used.
  • FIG. 7 provides a schematic example of a system including a tape for depositing nanomaterial onto a substrate.
  • the deposition of one or more nanomaterials onto a substrate is facilitated by pick up of a composition comprising nanomaterial, unpatterned or in a predetermined pattern, from a transfer surface (e.g., a cliche system as depicted) onto a surface of the tape 92 which is run through the system.
  • the nanomaterial is subsequently transferred to the substrate 98.
  • a presser 94 (examples of which include a roller (having e.g., circular or oval cross-section) or a stamp (examples of which are depicted in FIG. 6) or other suitable component may be used to press the tape against the transfer surface and/or to press the tape against the substrate.
  • the presser and tape act as an applicator to deposit nanomaterial onto the substrate.
  • the tape and presser can be selected to have dimensions selected such that the substrate can be fully patterned in a single process step.
  • the tape can optionally be a consumable or can be recycled. If recycled, the tape will preferable be clean before being reused.
  • this method can carried out in a continuous manner (e.g., roll to roll).
  • a tape can optionally further include a release layer or other surface treatment of the tape surface, tape dispensing components, post-use conditioning of the tape (dry or wet cleaning), etc.
  • the number, arrangement, shape, and size of the grooves of the transfer surface and the nanomaterials included therein will be selected according to the predetermined pattern to be deposited onto the substrate.
  • the one or more compositions comprising the nanomaterials to be deposited can be dispensed into the grooves by any of the above-discussed techniques or other suitable techniques for dispense compositions and/or nanomaterials onto a transfer surface.
  • a method utilizing a tape to deposit nanomaterial(s) onto the substrate is expected to provide increased scalability with respect to the sizes of the substrates to be patterned and also the number of surfaces to be processed per unit time.
  • the tape has sufficient thickness and/or rigidity to receive the composition, transfer the composition or nanomaterial, and be manipulated by the presser and tape handling components of the equipment.
  • a tape material comprises includes Kapton 200E, Kapton 300H, Kapton 500H, other Kapton materials, PET, TEONEX, silicone treated PET, etc.
  • Other examples include, but are not limited to, foil (including, but not limited to, metal foil), paper, nylon, cloth, the materials listed herein as examples of mask materials, cellulose based products, fabrics, plastics, including, for example, but not limited to, ABS, acetates, butyrates, phenolics, polycarbonates, polyesters, polyethylen ⁇ s, polypropylenes, polystyrenes, polyurethanes and polyvinyl chlorides as monomers, copolymers and/or laminates.
  • suitable materials and suppliers of such materials are available to those of ordinary skill in the art through various sources.
  • the selection of a tape material can depend upon the equipment being used in carrying out the method.
  • the dimensions of the tape material are preferably selected corresponding to the size of the substrate or printing area onto which nanomaterial is to be deposited.
  • a tape is in the form of a continuous roll, having a predetermined width and thickness.
  • the tape preferably has a release layer deposited on the face that will pick up the composition and deposit the composition and/or nanomaterial composition onto the substrate, depending on whether a wet or dry transfer is desired.
  • a coating include, Parylene, Parylene-C, Parylene-N, Parylene-F, Parylene-D, Parylene-HT, Parylene AF4, other parylene compositions, other surface modifying organic molecules, and other plastics, and other surface chemistry and/or other surface treatments (e.g., energetic treatments including, but not limited to, plasma treatment, laser treatment, etc.) known or recognized in the art.
  • the surface can be silanized.
  • deterioration e.g., abrasion-wear, flaking due to brittleness, etc.
  • the integrity of the layer e.g., the integrity of the attachment of the layer to the tape, smoothness of the layer, etc.
  • the shape and contour of the presser e.g., the radius of curvature of a stamps, the radius of curvature of the rollers, the tape path itself, etc.
  • the surface of the tape can be smooth (e.g., it does not include elevations and/or depressions). In other embodiments, the surface of the tape can include features (e.g., elevations and/or depressions).
  • a presser is not a flat surface that fully presses the tape against the substrate at a single time, to minimize trapped air between the tape and substrate when the composition or nanomaterial, as the case may be, is applied. Trapped air during the deposition step can result in an incomplete transfer.
  • one or more compositions are delivered to the uppermost surface of a transfer surface from above (by, e.g., an inkcup, a micro-dispenser, an array of micro-dispensers, etc.) or from below the transfer surface (by, e.g., use of a transfer surface with a reservoir below and in connection with the uppermost surface of the transfer surface).
  • a tape is passed over the uppermost surface of a transfer surface including at least one composition.
  • a first presser (depicted as a roller with a circular cross-section) rolls over the side of the tape remote from the transfer surface to press the underside of the tape (as depicted) against the uppermost surface of the transfer surface to transfer composition from the transfer surface to the tape.
  • the tape is advanced to align the composition on the tape for application to the substrate upon contact when pressed by a second presser (FIG. 8 D).
  • the patterned composition can be permitted to dry so that when the second presser presses the tape including the pattern against the substrate, patterned nanomaterial is transferred to the substrate.
  • the first and second pressers can have the same or different shapes and/or sizes. It is envisioned that a single presser could be moved relative to the tape, transfer surface, and substrate instead of using two applicators. Optionally the surface of the applicators) used can be patterned or featureless.
  • an unpattemed layer of one or more nanomaterials can be transferred to a tape from a smooth transfer surface and deposited onto the substrate by contacting the tape to the substrate.
  • FlG. 9 illustrates an alternative embodiment in which one or more compositions are delivered to a surface of the tape by inkjet printing.
  • a composition which includes a carrier which dissolves or otherwise reacts with the substrate
  • the use of inkjet printing to deliver the composition to the surface can reduce or remove the considerations of such reaction provided the vapor pressure of the carrier and/or ambient conditions facilitate evaporation of the carrier prior to transfer of the nanomaterial to the substrate.
  • FIG. 8 and 1 1 depict examples of embodiments that include a roller, a stamp or other device could alternatively be used to contact the tape to the transfer surface and/or the substrate.
  • Methods in accordance with the invention provide advantages that can be particularly useful, for example, in depositing semiconductor nanocrystals in the fabrication of a light-emitting device (LED) including semiconductor nanocrystals.
  • LED light-emitting device
  • the method of the invention can allow the patterned deposition of solution processable layers comprising nanomaterial (e.g., semiconductor nanocrystals, other na ⁇ oparticles, etc.) within a layered structure without disturbing the structure fidelity through the introduction of solvent to the device.
  • nanomaterial e.g., semiconductor nanocrystals, other na ⁇ oparticles, etc.
  • certain embodiments of the invention can be useful with existing backplane technology, and with off-the-shelf well known transport films.
  • the present invention is also expected to facilitate high throughput, since the nanomaterial can be introduced to the device in an singular process.
  • Various embodiments of the invention are also expected to be compatible with processes for the manufacture of flexible displays, whether, for example, by roll-to-roll or flex-on-rigid batch mode processing.
  • semiconductor nanocrystals have narrow emission linewidths, are photoluminescent efficient, and emission wavelength tunable, they can be a desirable lumophore.
  • the semiconductor nanocrystals optionally include organic ligands attached to the surface thereof. These zero-dimensional semiconductor structures show strong quantum confinement effects that can be harnessed in designing bottom-up chemical approaches to create complex heterostructures with electronic and optical properties that are tunable with the size and composition of the nanocrystals.
  • the size and composition of the semiconductor nanocrystals can be selected such that semiconductor nanocrystals emit photons at a predetermined wavelength of wavelength band in the far-visible, visible, infra-red or other desired portion of the spectrum.
  • the wavelength can be between 300 and 2,500 nm or greater, such as between 300 and 400 nm, between 400 and 700 nm, between 700 and 1100 nm, between 1100 and 2500 nm, or greater than 2500 nm.
  • the semiconductor nanocrystals can include semiconductor nanocrystals that emit light at the same or different wavelengths. By including an arrangement the semiconductor nanocrystals that emit light at different wavelengths, a multicolor pattern can be formed.
  • a multicolor pattern can optionally include a repeating pattern comprising two or more different semiconductor nanocrystal materials that emit light at different wavelengths.
  • each different color emitting nanomaterial can each independently include a plurality of semiconductor nanocrystals.
  • the method can include introducing onto a transfer surface a first nanomaterial including a plurality of semiconductor nanocrystals having an emission wavelength distinguishable from a second nanomaterial including a plurality of semiconductor nanocrystals.
  • the method can further include introducing a third or more nanomaterial s, each including a plurality of semiconductor nanocrystals, on a transfer surface.
  • Each of the third or more nanomaterials comprises a plurality of semiconductor nanocrystals that can have an emission wavelength distinguishable from that of the other nanomaterials.
  • the first, second, third, and other nanomaterials including pluralities of semiconductor nanocrystals can be applied to the same or different transfer surfaces, in either case, to be deposited in overlapping or non-overlapping predefined regions of the substrate.
  • the emission wavelengths of the first, second, third, and other nanomaterials comprising pluralities of semiconductor nanocrystals can be selected from an ultraviolet, blue, green, yellow, red, cyan, magenta, infrared emission, or other wavelength, or a combination thereof.
  • a feature of the pattern can have a dimension of less than 10 millimeters, less than 1 millimeter, less than 100 micrometers, or less than 1 micrometer.
  • a feature of the pattern can have a dimension of at least I centimeter, at least 10 centimeters, or at least 100 centimeters.
  • the surface to which the semiconductor nanocrystals are applied is typically a substrate which includes one or more device layers in-between the substrate surface and patterned semiconductor nanocrystals. Additional device layers are typically subsequently disposed over the nanocrystals. Individual saturated color LEDs can be formed at multiple locations on a single substrate to form a display.
  • the substrate can include a layer including a hole transport material over the electrode.
  • the method can include forming a layer including an electron transporting material over the nanomaterial.
  • a second electrode can be applied over the layer including an electron transporting material.
  • An embodiment of the invention including a dry transfer process of at least the nanomaterials from the tape to the device structure is preferred when transferring semiconductor nanocrystals to an organic layer of a light-emitting device structure during device fabrication.
  • the possible reaction of the liquid of the composition with the inorganic layer can be less of a concern.
  • the semiconductor nanocrystals are deposited at a thickness of multiple monolayers or less, e.g., greater than three monolayers, three or less monolayers, two or less monolayers, a single monolayer, a partial monolayer, etc.
  • the thickness of each deposited layer of semiconductor nanocrystals may vary.
  • the variation of the thickness at any point of the deposited nanocrystals is less than three monolayers, more preferably less than two monolayers, and most preferably less than one monolayer.
  • the substrate can include a backplane.
  • the backplane includes active or passive electronics for controlling or switching power to individual pixels.
  • Including a backplane can be useful for applications such as displays, sensors, or imagers.
  • the backplane can be configured as an active matrix, passive matrix, fixed format, direct drive, or hybrid.
  • the display can be configured for still images, moving images, or lighting.
  • a lighting display can provide white light, monochrome light, or color-tunable light.
  • the deposition method is scalable, and can allow inexpensive manufacturing of LEDs over a large surface area.
  • semiconductor nanocrystals are included in a light emitting device at a monolayer thickness.
  • a monolayer can provide the beneficial light emission properties of semiconductor nanocrystals while minimizing the impact on electrical performance.
  • a light emitting device can include two layers separating two electrodes of the device.
  • the material of one layer can be chosen based on the material's ability to transport holes, or the hole transporting layer (HTL).
  • the material of the other layer can be chosen based on the material's ability to transport electrons, or the electron transporting layer (ETL).
  • the electron transporting layer typically includes an electroluminescent layer. When a voltage is applied, one electrode injects holes (positive charge carriers) into the hole transporting layer, while the other electrode injects electrons into the electron transporting layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an exciton is formed, which can recombine to emit light.
  • Nanocrystals having small diameters can have properties intermediate between molecular and bulk forms of matter. For example, nanocrystals based on semiconductor materials having small diameters can exhibit quantum confinement of both the electron and hole in all three dimensions, which leads to an increase in the effective band gap of the material with decreasing crystallite size. Consequently, both the optical absorption and emission of nanocrystals shift to the blue, or to higher energies, as the size of the crystallites decreases.
  • the emission from the nanocrystal can be a narrow Gaussian emission band that can be tuned through the complete wavelength range of the ultraviolet, visible, or infrared regions of the spectrum by varying the size of the nanocrystal, the composition of the nanocrystal, or both.
  • CdSe can be tuned in the visible region
  • InAs can be tuned in the infrared region.
  • the narrow size distribution of a population of nanocrystals can result in emission of light in a narrow spectral range.
  • the population can be monodisperse and can exhibit less than a 15% rms deviation in diameter of the nanocrystals, preferably less than 10%, more preferably less than 5%.
  • Spectral emissions in a narrow range of no greater than about 75 nm, preferably 60 nm, more preferably 40 nm, and most preferably 30 nm full width at half max (FWHM) can be observed.
  • the breadth of the emission decreases as the dispersity of nanocrystal diameters decreases.
  • Semiconductor nanocrystals can have high emission quantum efficiencies such as greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%.
  • a light emitting device can have a structure such as shown in FlG. 10, in which a first electrode 1302, a first layer 1303 in contact with the electrode 1302, a second layer 1304 in contact with the layer 1303, and a second electrode 1305 in contact with the second layer 1304.
  • First layer 1303 can be a hole transporting layer and second layer 1304 can be an electron transporting layer. At least one layer can be non-polymeric. Alternatively, a separate emissive layer (not shown in FIG. 10) can be included between the hole transporting layer and the electron transporting layer.
  • One of the electrodes of the structure is in contact with a substrate 1301. Each electrode can contact a power supply to provide a voltage across the structure.
  • Electroluminescence can be produced by the emissive layer of the heterostructure when a voltage of proper polarity is applied across the heterostructure.
  • First layer 1303 can include a plurality of semiconductor nanocrystals, for example, a substantially monodisperse population of nanocrystals.
  • a separate emissive layer can include the plurality of nanocrystals.
  • a layer that includes semiconductor nanocrystals is preferably a monolayer of nanocrystalSi
  • the substrate can be opaque or transparent.
  • the substrate can be rigid or flexible.
  • the substrate can be plastic, metal or glass.
  • the first electrode can be, for example, a high work function hole-injecting conductor, such as an indium tin oxide (ITO) layer.
  • ITO indium tin oxide
  • Other first electrode materials can include gallium indium tin oxide, zinc indium tin oxide, titanium nitride, or polyaniline.
  • the second electrode can be, for example, a low work function (e.g., less than 4.0 eV), electron- injecting, metal, such as Al, Ba, Yb, Ca, a lithium-aluminum alloy (Li:Al), or a magnesium-silver alloy (Mg:Ag).
  • the second electrode such as Mg:Ag
  • an opaque protective metal layer for example, a layer of Ag for protecting the cathode layer from atmospheric oxidation, or a relatively thin layer of substantially transparent ITO.
  • the first electrode can have a thickness of about 500 Angstroms to 4000 Angstroms.
  • the first layer can have a thickness of about 50 Angstroms to about 1000 Angstroms.
  • the second layer can have a thickness of about 50 Angstroms to about 1000 Angstroms.
  • the second electrode can have a thickness of about 50 Angstroms to greater than about 1000 Angstroms.
  • the electron transporting layer can be a molecular matrix.
  • the molecular matrix can be non-polymeric.
  • the molecular matrix can include a small molecule, for example, a metal complex.
  • the metal complex can be a metal complex of 8-hydroxyquinoline.
  • the metal complex of 8-hydroxyquinoline can be an aluminum, gallium, indium, zinc or magnesium complex, for example, aluminum tris(8-hydroxyquinoline) (AIq 3 ).
  • Other classes of materials in the ETL can include metal thioxinoid compounds, oxadiazole metal chelates, triazoles, sexithiophene derivatives, pyrazine, and styrylanthracene derivatives.
  • the hole transporting layer can include an organic chromophore.
  • the organic chromophore can be a phenyl amine, such as, for example, N,N'- diphenyl-N,N'-bis(3-methylphenylKl,l'-biphenyl)-4,4'-diamine (TPD), 4-4'-N,N'-dicarbazolyl- biphenyl (CBP), 4,4-. bis[N-(l-naphthyl)-N-phenylamino]biphenyl (NPD), etc.
  • the HTL can include a polyaniline, a polypyrrole, a poly(phenylene vinylene), copper phthalocyanine, an aromatic tertiary amine or polynuclear aromatic tertiary amine, a 4,4'-bis(9-carbazolyl)-l,l'-biphenyl compound, or an N,N,N',N'-tetraarylbenzidine.
  • the layers can be deposited on a surface of one of the electrodes by spin coating, dip coating, vapor deposition, or other thin film deposition methods. See, for example, M. C. Schlamp, et al, J. Appl. Phys., 82, 5837-5842, (1997); V. Santhanam, et al., Langmuir, 19, 7881-7887, (2003); and X. Lin, et al., J. Phys. Chem. B, 105, 3353-3357, (2001), each of which is incorporated by reference in its entirety.
  • the second electrode can be sandwiched, sputtered, or evaporated onto the exposed surface of the solid layer. One or both of the electrodes can be patterned.
  • the electrodes of the device can be connected to a voltage source by electrically conductive pathways. Upon application of the voltage, light is generated from the device.
  • semiconductor nanocrystals are processed in a controlled (oxygen-free and moisture-free) environment, preventing the quenching of luminescent efficiency during the fabrication process.
  • a blocking layer such as an electron blocking layer (EBL), a hole blocking layer (HBL) or a hole and electron blocking layer (eBL), can be introduced in the structure.
  • EBL electron blocking layer
  • HBL hole blocking layer
  • eBL hole and electron blocking layer
  • a blocking layer can include 3-(4-biphenylyl)-4-phenyl-5-tert- butylphenyl-l,2,4-triazole (TAZ), 3,4,5-triphenyl-l,2,4-triazole, 3,5-bis(4-tert-butylphenyl)-4- phenyl-l,2,4-triazole, bathocuproine (BCP), 4,4',4"-tris ⁇ N-(3-methylphenyl)-N- phenylamino ⁇ triphenylamine (m-MTDATA), polyethylene dioxythiophene (PEDOT), 1 ,3-bis(5-(4- diphenylamino)phenyl-l,3,4-oxadiazol-2-yl)benzene, 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-l,3,4- oxadiazole, 1 ,3 -bis[5-(4-( 1 , 1
  • a detailed example of one embodiment of a device structure can include a 150 nm indium tin oxide (ITO) anode layer, a 70 nm Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT.PSS) hole injection layer (HIL), a 50 nm N,N'-Bis(3- methylphenyl)-N,N'-bis-(phenyl)-spiro (spiro-TPD) hole transport layer, a 5-10 nm semiconductor nanocrystal emissive layer, a 50 nm 2,2',2"-(l,3,5-benzinetriyl)- tris(l -phenyl- 1 -H-benzimidazole) (TPBi) hole-blocking/electron transporting layer and a 0.5 nm LiF/100 nm Al cathode layer.
  • ITO indium tin oxide
  • PEDOT.PSS Poly(3,
  • the ITO layer can be deposited, patterned and cleaned using industry standard techniques.
  • the PEDOTrPSS layer can be deposited by spin coating followed by bake out at 125 C for 20 minutes.
  • AU other organic and metal layers can be thermally evaporated in a high vacuum chamber.
  • the entire device Prior to testing and operation the entire device is preferably encapsulated using, for example, a sealant in a dry nitrogen environment ( ⁇ 1 ppm O 2 , ⁇ 1 ppm H 2 O).
  • a sealant of the type used in OLEDs is one example of a sealant that can be used.
  • Examples of semiconductor nanocrystals useful in the above described device include, for example, and without limitation, those described in U.S. Patent Application Nos. 60/825373, filed 12 September 2006 and 60/825374m filed 12 September 2006.
  • the performance of light emitting devices can be improved by increasing their efficiency, narrowing or broadening their emission spectra, or polarizing their emission. See, for example, Bulovic et al., Semiconductors and Semimetals 64, 255 (2000), Adachi et al., Appl. Phys. Lett. 78, 1622 (2001), Yamasaki et al., Appl. Phys. Lett. 76, 1243 (2000), Dirr et al., Jpn. J. Appl. Phys. 37, 1457 (1998), and D'Andrade et al., MRS Fall Meeting, BB6.2 (2001 ), each of which is incorporated herein by reference in its entirety.
  • Nanocrystals can be included in efficient hybrid organic/inorganic light emitting devices.
  • the narrow FWHM of nanocrystals can result in saturated color emission. This can lead to efficient nanocrystal-light emitting devices even in the red and blue parts of the visible spectrum, since in nanocrystal emitting devices no photons are lost to infrared and UV emission.
  • the broadly tunable, saturated color emission over the entire visible spectrum of a single material system is unmatched by any class of organic chromophores (see, for example, Dabbousi et al, J. Phys. Chem. 101 , 9463 (1997), which is incorporated by reference in its entirety).
  • a monodisperse population of nanocrystals will emit light spanning a narrow range of wavelengths.
  • a device including more than one size of nanocrystal can emit light in more than one narrow range of wavelengths.
  • the color of emitted light perceived by a viewer can be controlled by selecting appropriate combinations of nanocrystal sizes and materials in the device.
  • the degeneracy of the band edge energy levels of nanocrystals facilitates capture and radiative recombination of all possible excitons, whether generated by direct charge injection or energy transfer.
  • the maximum theoretical nanocrystal-light emitting device efficiencies are therefore comparable to the unity efficiency of phosphorescent organic light emitting devices.
  • the excited state lifetime ( ⁇ ) of the nanocrystal is much shorter ( ⁇ ⁇ 10 ns) than a typical phosphor ( ⁇ > 0.5 ⁇ s), enabling nanocrystal-light emitting devices to operate efficiently even at high current density.
  • Devices can be prepared that emit visible or infrared light.
  • the size and material of a semiconductor nanocrystal can be selected such that the nanocrystal emits visible or infrared light of a selected wavelength.
  • the wavelength can be between 300 and 2,500 nm or greater, for instance between 300 and 400 nm, between 400 and 700 nm, between 700 and 1 100 nm, between 1 100 and 2500 nm, or greater than 2500 nm.
  • Individual devices can be formed at multiple locations on a single substrate to form a display.
  • the display can include devices that emit at different wavelengths.
  • methods in accordance with the invention can be used to deposit various other materials, especially other materials comprising nanoparticles, in fabricating a variety of lighting, electronic, or optoelectronic devices.
  • an unpatterned layer comprising nanomaterial comprising a white light- emitting mixture of semiconductor nanocrystals can be deposited onto a substrate by a method in accordance with the invention.
  • the mixture includes semiconductor nanocrystals with different sizes and compositions which can simultaneously emit light at different wavelengths to achieve white light emission.
  • the mixture of semiconductor nanocrystals are deposited as a layer in a device structure that also includes a hole transport layer and/or an electron transport layer.
  • the device may used to provide general lighting or may be included in a display, e.g., a liquid crystal display, to provide backlighting. Alternatively, the device may further include a color filter to provide a full-color display. See U.S. Patent Application No.
  • a photodetector device includes one or more nanomaterials comprising a plurality of semiconductor nanocrystals which are selected based upon absorption properties.
  • semiconductor nanocrystals are engineered to produce a predetermined electrical response upon absorption of a particular wavelength, typically in the IR or MIR region of the spectrum.
  • photodetector devices including semiconductor nanocrystals are described in "A Quantum Dot Heterojunction Photodetector" by Alexi Cosmos Arango, Submitted to the Department of Electrical Engineering and Computer Science, in partial fulfillment of the requirements for the degree of Masters of Science in Computer Science and Engineering at the Massachusetts Institute of Technology, February 2005, the disclosure of which is hereby incorporated herein by reference in its entirety.
  • a method of fabricating photodetector device includes applying a layer including nanomaterial to a surface of a tape from a transfer surface and depositing nanomaterial onto a substrate.
  • the nanomaterial including a plurality of semiconductor nanocrystals can be deposited on the substrate as an unpatterned layer.
  • a method of fabricating an array of photodetector devices includes applying a layer comprising nanomaterial to surface of a tape from a transfer surface and depositing nanomaterial onto a substrate.
  • the nanomaterial including a plurality of semiconductor nanocrystals can be deposited on the substrate as a patterned layer.
  • the substrate can further include an electrode.
  • a second electrode can be deposited over the nanomaterial.
  • an electron transport layer can be included between the nanomaterial and the cathode electrode and/or a hole transport layer can be included between the anode electrode and the nanomaterial.
  • a method of fabricating a photodetector device or array of devices can optionally include depositing one or more nanomaterials in a predetermined arrangement (patterned or unpatterned). As discussed above, nanomaterial can optionally be included in a composition.
  • Methods in accordance with the invention can also be used in deposition nanomaterials in the fabrication of memory devices.
  • An example of a nonvolatile device is described in U.S. Patent Application No. 10/958,659, entitled “Non- Volatile Memory Device", of Bawendi et al., filed 6 October 2004, the disclosure of which is hereby incorporated herein by reference in its entirety.
  • nanomaterial can optionally be included in a composition.
  • top and bottom are relative positional terms, based upon a location from a reference point.
  • top of a device structure means farthest away from the substrate, while “bottom” means closest to the substrate.
  • bottom electrode is the electrode closest to the substrate, and is generally the first electrode fabricated; the top electrode is the electrode that is more remote from the substrate, on the top side of the light-emitting material.
  • the bottom electrode has two surfaces, a bottom surface closest to the substrate, and a top surface further away from the substrate.
  • a first layer is described as disposed or deposited “over” a second layer, the first layer is disposed further away from substrate.
  • a cathode may be described as "disposed over” an anode, even though there are various organic and/or inorganic layers in between.
  • the singular forms "a”, “an” and “the” include plural unless the context clearly dictates otherwise.
  • reference to an emissive material includes reference to one or more of such materials.
  • nanocrystal In various instances herein, a semiconductor nanocrystal is referred to by the term "nanocrystal".

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Abstract

Methods for depositing material and nanomaterial onto a substrate are disclosed. Also disclosed are methods of making devices including nanomaterials, and a system useful for depositing materials and nanomaterials.

Description

METHODS OF DEPOSITING NANOMATERIAL & METHODS OF MAKING A DEVICE
CLAIM OF PRIORITY
This application claims priority to U.S. Application Nos.: 60/790,393 filed 7 April 2006; 60/792,086 filed 14 April 2006; and 60/792,170 filed 14 April 2006; each of the foregoing being hereby incorporated herein by reference in its entirety.
TECHNICAL FIELD OF THE INVENTION
The invention relates to compositions and methods of depositing same. More particularly, the invention relates to compositions including nanomaterial, methods and systems for depositing same.
BACKGROUND OF THE INVENTION
A number of industries, e.g., electronics, displays, lighting, optoelectronics, and energy industries, rely on the formation of layers, coatings and/or patterns of materials to form pixels, circuits, and other features on substrates. The primary methods for generating these patterns are screen printing for features larger than about 100 microns and thin film and etching methods for features smaller than about 100 microns. Other subtractive methods to attain fine feature sizes include the use of photo-patternable pastes and laser trimming.
SUMMARY OF THE INVENTION
It has been recognized that it would be advantageous to develop improved methods, systems, devices, and compositions for depositing nanomaterials onto a substrate.
In accordance with one aspect of the invention, there is provided a method for depositing nanomaterial onto a substrate. The method comprises applying a composition comprising nanomaterial to a surface of a tape, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate.
In accordance with another aspect of the invention, there is provided a method for depositing nanomaterial onto a substrate. The method comprises applying a composition comprising nanomaterial to a surface of a tape from a transfer surface, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate.
The nanomaterial can be included in a composition which may or may not include further components. In certain detailed aspects, the composition can further include a liquid or other carrier medium. The composition can optionally include one or more additional components. A nanomaterial typically includes nanoparticles having an average maximum dimension smaller than 100 nm. Examples of nanoparticles include, for example, a semiconductor nanocrystal, a nanotube (such as a single walled or multi-walled carbon nanotube), a nanowire, a nanorod, a dendrimer, organic nanocrystal, organic small molecule, other nano-scale or micro-scale material or mixtures thereof.
In certain embodiments, nanomaterial includes semiconductor nanocrystals. Semiconductor nanocrystals comprise nanometer-scale inorganic semiconductor particles. Semiconductor nanocrystals preferably have an average nanocrystal diameter less than about ISO Angstroms (A), and most preferably in the range of 12-150 A.
In accordance with another aspect of the invention, there is provided a method of making a light emitting device. The method comprises applying a composition comprising semiconductor nanocrystals to a surface of a tape, and contacting the surface of the tape including the semiconductor nanocrystals to the substrate under conditions to cause at least a portion of the semiconductor nanocrystals to deposit onto the substrate.
In accordance with still another aspect of the invention, there is provided a method of forming a device. The method comprises applying a composition comprising nanomaterial to a surface of a tape; contacting the surface of the tape including the nanomaterial to a substrate a substrate including a first electrode under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate; and arranging a second electrode opposed to the first electrode.
In certain embodiments of the methods of the invention, the tape including nanomaterial can be divided into sheets of predetermined size prior to being contacted to the substrate. In certain embodiments the size of the sheet corresponds to the size of the substrate onto which nanomaterial is to be deposited. In certain embodiments the size of the sheet corresponds to the size of a predetermined area of the substrate onto which nanomaterial is to be deposited. Other aspects of the invention include systems and articles for transferring a nanomaterial to a surface.
The foregoing, and other aspects described herein all constitute embodiments of the present invention.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed. Other embodiments will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIGS. 1 A-B are diagrams depicting examples of an embodiment of a transfer surface including a pattern of grooves.
FIGS. 2 A-B are diagrams depicting examples of embodiments including a mask.
FIG. 3 is a diagram depicting an example of a technique for dispensing one or more compositions to a transfer surface.
FIG. 4 illustrates an example of a technique for dispensing one or more compositions to a transfer surface.
FIG. S is a diagram depicting an example of a method of the invention including a tape.
FIG. 6 are diagrams depicting examples of applicators for use in various embodiments of a method of the invention.
FIG. 7 is diagram depicting an example of a system for use in various embodiments of a method of the invention.
FIGS. 8 A-D are diagrams depicting an example of a system including a transfer surface and tape for use in various embodiments of a method of the invention. FIG. 9 is a diagram depicting an example of a system including a tape for use in various embodiments of a method of the invention.
FIG. 10 is a schematic drawing depicting a light-emitting device.
The attached figures are simplified representations presented for purposed of illustration only; the actual structures may differ in numerous respects, including, e.g., relative scale, etc.
For a better understanding to the present invention, together with other advantages and capabilities thereof, reference is made to the following disclosure and appended claims in connection with the above-described drawings.
DETAILED DESCRIPTION OF THE INVENTION
One aspect of the invention relates to a method for depositing material onto a substrate.
Another aspect of the invention related to methods for depositing nanomaterial onto a substrate.
In accordance with one aspect of the invention, there is provided a method for depositing nanomaterial onto a substrate. The method comprises applying a composition comprising nanomaterial to a surface of a tape, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate. Known techniques can be used to transfer the layer comprising nanomaterial from the tape surface to the substrate. Examples include, but are not limited to, application of pressure, laser writing, laser ablation, thermal transfer, and other techniques identifiable by a person of ordinary skill in the relevant art.
In certain embodiments, a mask can be positioned on the substrate prior to contacting the surface of the tape comprising nanomaterial to the substrate.
The nanomaterial can optionally be included in a composition. The composition can further include a liquid or other carrier medium. The composition can further include one or more additional components. A nanomaterial typically includes nanoparticles having an average maximum dimension smaller than 100 nm.
Examples of nanoparticles include, for example, a semiconductor nanocrystal, a nanotube (such as a single walled or multi-walled carbon nanotube), a naπowire, a nanorod, a dendrimer, organic nanocrystal, organic small molecule, other nano-scale or micro-scale material or mixtures thereof.
Nanomaterial particles can have various shapes, including, but not limited to, sphere, rod, disk, other shapes, and mixtures of various shaped particles.
Examples of organic nanocrystal s include, without limitation, J-aggregates, H-aggregates, and organic nanocrystals including aggregates with other dipole arrangements. Examples of organic nanocrystals are described in S. Kirstein et al., "Herringbone Structures In Two- Dimensional Single Crystals of Cyanine Dyes. I. Detailed Structure Analysis Using Electron Diffraction", J. Chem. Phys. 103(2) July 1995, pages 816 et seq.; S. Kirstein et al., "Herringbone Structures In Two- Dimensional Single Crystals of Cyanine Dyes. II. Optical Properties", J. Chem. Phys. 103(2) July 1995, pages 826 et seq.; A. Mishra et al. "Cyanines During the 1990s: A Review", Chem. Rev. 2000, 100, 1973-201 1 ; and C. Peyratout et al., "Aggregation of Thiacyanine Derivatives On Polyelectrolytes:, Phys. Chem. Chem. Phys., 2002, 4, 3032-3039, the disclosures of which are hereby incorporated herein by reference in their entireties.
The present invention is useful for depositing nanomaterials, including, but not limited to, nanomaterials with optical and/or electronic characteristics, in patterned or unpatterned arrangements.
A nanomaterial can include one nanomaterial or a mixture of two or more different nanomaterials. Nanomaterials can be different based on, e.g. chemical composition, particle morphology (e.g., size, shape, surface area, particle size distribution, Full Width at Half-Maximum (FWHM), etc.), surface treatment(s) (e.g., not surface-modified, surface modified, and if surface modified, the details of the surface modification (e.g., composition, etc.)), particle structure (e.g., uncoated or coated; and if coated, the details of the coating, e.g., composition, thickness, nature of the coating (e.g., continuous, non-continuous, particulate, film, etc.)), performance characteristics (e.g., absorption properties, emission characteristics, etc.) of each nanomaterial, different combinations of chemical, physical, and/or performance aspects, etc. In certain embodiments, nanomaterial includes semiconductor nanocrystals. Semiconductor nanocrystals comprise nanometer— scale inorganic semiconductor particles. Semiconductor nanocrystals preferably have an average nanocrystal diameter less than about ISO Angstroms (A), and most preferably in the range of 12-150 A.
In certain embodiments, inorganic semiconductor nanocrystals comprise Group IV elements, Group II-VI compounds, Group H-V compounds, Group III-VI compounds, Group III-V compounds, Group IV-VI compounds, Group I-III-VI compounds, Group II-IV-VI compounds, or Group H-IV-V compounds, alloys thereof and/or mixtures thereof, including ternary and quaternary alloys and/or mixtures. Examples include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, GaSe, InN, InP, InAs, InSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, Si, Ge, alloys thereof and/or mixtures thereof, including ternary and quaternary alloys and/or mixtures.
In certain embodiments, semiconductor nanocrystals preferably include a "core" of one or more first semiconductor materials, which may be surrounded by an overcoating or "shell" of a second semiconductor material. A semiconductor nanocrystal core surrounded by a semiconductor shell is also referred to as a "core/shell" semiconductor nanocrystal.
For example, the semiconductor nanocrystal can include a core having the formula MX, where M is cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, thallium, or mixtures thereof, and X is oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, or mixtures thereof. Examples of materials suitable for use as semiconductor nanocrystal cores include, but are not limited to, CdS, CdO, CdSe, CdTe, ZnS, ZnO, ZnSe, ZnTe, MgTe, GaAs, GaP, GaSb, GaN, HgS, HgO, HgSe, HgTe, InAs, InP, InSb, InN, AlAs, AlP, AlSb, AIS, PbS, PbO, PbSe, Ge, Si, alloys thereof, and/or mixtures thereof, including ternary and quaternary alloys and/or mixtures. Other non-limiting examples are provided above, Examples of materials suitable for use as semiconductor nanocrystal shells include, but are not limited to, CdS, CdO, CdSe, CdTe, ZnS, ZnO, ZnSe, ZnTe, MgTe, GaAs, GaP, GaSb, GaN, HgS, HgO, HgSe, HgTe, InAs, InP, InSb, InN, AlAs, AIP, AlSb, AIS, PbS, PbO, PbSe, Ge, Si, alloys thereof, and/or mixtures thereof, including ternary and quaternary alloys and/or mixtures. Other non-limiting examples are provided above.
In certain embodiments, the surrounding "shell" material can have a bandgap greater than the bandgap of the core material. In certain embodiments, the shell can be chosen so as to have an atomic spacing close to that of the "core" substrate. In certain embodiments, the surrounding shell material can have a bandgap less than the bandgap of the core material. In a further embodiment, the shell and core materials can have the same crystal structure. Examples of semiconductor nanocrystals (core)shell structures include, without limitation: (CdSe)ZnS (core)shell, (CdZnSe)CdZnS (core)shell, and (CdS)CdZnS (core)shell.
For further examples of core/shell semiconductor structures, see U.S. Application No. 10/638,546, entitled "Semiconductor Nanocrystal Heterostructures", filed 12 August 2003, which is hereby incorporated herein by reference in its entirety.
The semiconductor nanocrystals are preferably members of a population of semiconductor nanocrystals having a narrow size distribution. More preferably, the semiconductor nanocrystals comprise a monodisperse or substantially monodisperse population of semiconductor nanocrystals. The monodisperse distribution of diameters can also be referred to as a size. In certain embodiments, the monodisperse population of semiconductor nanocrystals exhibits less than a 15% rms deviation in diameter of the nanocrystals, preferably less than 10%, more preferably less than 5%.
Methods of preparing monodisperse semiconductor nanocrystals include pyrolysis of organometallic reagents, such as dimethyl cadmium, injected into a hot, coordinating solvent. This permits discrete nucleation and results in the controlled growth of macroscopic quantities of nanocrystals. Preparation and manipulation of semiconductor nanocrystals are described, for example, in U.S. Patent 6,322,901 and 6,576,291, and U.S. Patent Application No. 60/550,314, each of which is hereby incorporated herein by reference in its entirety. Additional examples of methods of preparing semiconductor nanocrystal are described in U.S. Patent Application No. 11/354185 of Bawendi et al., entitled "Light Emitting Devices Including Semiconductor Nanocrystals", filed 15 February 2006, and U.S. Patent Application No. 1 1/253595 of Coe-Sullivan et al., entitled "Light Emitting Device Including Semiconductor Nanocrystals", filed 21 October 2005, and U.S. Patent Application No. 10/638546 of Kim et al., entitled "Semiconductor Nanocrystal Heterostructures", filed 12 August 2003, referred to above, each of which is hereby incorporated by reference herein in its entirety.
One method of manufacturing a nanocrystal comprises a colloidal growth process. Colloidal growth occurs by rapidly injecting an M donor and an X donor into a hot coordinating solvent. The injection produces a nucleus that can be grown in a controlled manner to form a nanocrystal. The reaction mixture can be gently heated to grow and anneal the nanocrystal. Both the average size and the size distribution of the nanocrystals in a sample are dependent on the growth temperature. The growth temperature necessary to maintain steady growth increases with increasing average crystal size. The nanocrystal is a member of a population of nanocrystals. As a result of the discrete nucleation and controlled growth, the population of nanocrystals obtained has a narrow, monodisperse distribution of diameters. The monodisperse distribution of diameters can also be referred to as a size. The process of controlled growth and annealing of the nanocrystals in the coordinating solvent that follows nucleation can also result in uniform surface derivatization and regular core structures. As the size distribution sharpens, the temperature can be raised to maintain steady growth. By adding more M donor or X donor, the growth period can be shortened.
The M donor can be an inorganic compound, an organometallic compound, or elemental metal. M is cadmium, zinc, magnesium, mercury, aluminum, gallium, indium or thallium. The X donor is a compound capable of reacting with the M donor to form a material with the general formula MX. Typically, the X donor is a chalcogenide donor or a pnictide donor, such as a phosphine chalcogenide, a bis(silyl) chalcogenide, dioxygen, an ammonium salt, or a tris(silyl) pnictide. Suitable X donors include dioxygen, bis(trimethylsilyl) selenide ((TMS)2Se), trialkyl phosphine selenides such as (tri-n-octylphosphine) selenide (TOPSe) or (tri-n-butylphosphine) selenide (TBPSe), trialkyl phosphine tellurides such as (tri-n-octylphosphine) telluride (TOPTe) or hexapropylphosphorustriamide telluride (HPPTTe), bis(trimethylsilyl)telluride ((TMS)2Te); bis(trimethylsilyl)sulfϊde ((TMS)2S), a trialkyl phosphine sulfide such as (tri-n-octylphosphine) sulfide (TOPS), an ammonium salt such as an ammonium halide (e.g., NH4Cl), tris(trimethylsilyl) phosphide ((TMS)3P), tris(trimethylsilyl) arsenide ((TMS)3As), or tris(trimethylsilyl) antimonide ((TMS)3Sb). In certain embodiments, the M donor and the X donor can be moieties within the same molecule.
A coordinating solvent can help control the growth of the nanocrystal. The coordinating solvent is a compound having a donor lone pair that, for example, has a lone electron pair available to coordinate to a surface of the growing nanocrystal. Solvent coordination can stabilize the growing nanocrystal. Typical coordinating solvents include alkyl phosphines, alkyl phosphine oxides, alkyl phosphonic acids, or alkyl phosphinic acids, however, other coordinating solvents, such as pyridines, furans, and amines may also be suitable for the nanocrystal production. Examples of suitable coordinating solvents include pyridine, tri-n-octyl phosphine (TOP), tri-n-octyl phosphine oxide (TOPO) and tris-hydroxylpropylphosphine (tHPP). Technical grade TOPO can be used. In certain embodiments, a non-coordinating solvent can be used.
Size distribution during the growth stage of the reaction can be estimated by monitoring the absorption line widths of the particles. Modification of the reaction temperature in response to changes in the absorption spectrum of the particles allows the maintenance of a sharp particle size distribution during growth. Reactants can be added to the nucleation solution during crystal growth to grow larger crystals. By stopping growth at a particular nanocrystal average diameter and choosing the proper composition of the semiconducting material, the emission spectra of the nanocrystals can be tuned continuously over the wavelength range of 300 nm to 5 microns, or from 400 nm to 800 nm for CdSe and CdTe. The nanocrystal has a diameter of less than 150 A. A population of nanocrystals has average diameters in the range of 15 A to 125 A.
A semiconductor nanocrystal can have various shapes, including, but not limited to, sphere, rod, disk, other shapes, and mixtures of various shaped particles.
As discussed above, in certain embodiments, semiconductor nanocrystal can include a core/shell structure. In such embodiments, a semiconductor nanocrystal can include a core of a semiconductor material. A semiconductor nanocrystal core can comprise, for example, and without limitation, a semiconductor material represented by the formula MX, where M is cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, thallium, or mixtures thereof, and X is oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, or mixtures thereof. Other examples are provided elsewhere herein.
In embodiments including a core/shell structure, the core includes a shell (also referred to as an overcoating) on a surface of the core. The overcoat of a semiconductor material on a surface of the nanocrystal core can include for example, and without limitation, Group FV elements, Group II- VI compounds, Group H-V compounds, Group III-VI compounds, Group IH-V compounds, Group rV-VI compounds, Group I-III-VI compounds, Group H-FV-VI compounds, and Group H-IV-V compounds, for example, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, GaSe, InN, InP, InAs, InSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, or mixtures thereof. Other examples are provided elsewhere herein.
For example, ZnS, ZnSe or CdS overcoatings can be grown on CdSe or CdTe nanocrystals. An overcoating process is described, for example, in U.S. Patent 6,322,901. By adjusting the temperature of the reaction mixture during overcoating and monitoring the absorption spectrum of the core, over coated materials having high emission quantum efficiencies and narrow size distributions can be obtained. In certain embodiments, the overcoating can be between 1 and 10 monolayers thick. The particle size distribution can be further refined by size selective precipitation with a poor solvent for the nanocrystals, such as methanol/butanol as described in U.S. Patent 6,322,901. For example, nanocrystals can be dispersed in a solution of 10% butanol in hexane. Methanol can be added dropwise to this stirring solution until opalescence persists. Separation of supernatant and flocculate by centrifugation produces a precipitate enriched with the largest crystallites in the sample. This procedure can be repeated until no further sharpening of the optical absorption spectrum is noted. Size-selective precipitation can be carried out in a variety of solvent/nonsolvent pairs, including pyridine/hexane and chloroform/methanol. The size-selected nanocrystal population can have no more than a 15% rms deviation from mean diameter, preferably 10% rms deviation or less, and more preferably 5% rms deviation or less.
In certain embodiments, semiconductor nanocrystals are optionally surface modified, including, but not limited to, for example, having one or more ligand groups attached thereto.
In one embodiment, the ligands are derived from the coordinating solvent used during the growth process. The surface can be modified by repeated exposure to an excess of a competing coordinating group to form an overlayer. For example, a dispersion of the capped semiconductor nanocrystal can be treated with a coordinating organic compound, such as pyridine, to produce crystallites which disperse readily in pyridine, methanol, and aromatics but no longer disperse in aliphatic solvents. Such a surface exchange process can be carried out with any compound capable of coordinating to or bonding with the outer surface of the semiconductor nanocrystal, including, for example, phosphines, thiols, amines and phosphates. The semiconductor nanocrystal can be exposed to short chain polymers which exhibit an affinity for the surface and which terminate in a moiety having an affinity for a suspension or dispersion medium. Such affinity improves the stability of the suspension and discourages flocculation of the semiconductor nanocrystal. Nanocrystal outer layers are described in U.S. Patent 6,251,303, which is incorporated by reference in its entirety.
More specifically, the coordinating ligand can have the formula:
Figure imgf000011_0001
wherein k is 2, 3 or 5, and n is 1, 2, 3, 4 or 5 such that k-n is not less than zero; X is O, S, S=O, SO2, Se, Se=O, N, N=O, P, P=O, As, or As=O; each of Y and L, independently, is aryl, heteroaryl, or a straight or branched C2-H hydrocarbon chain optionally containing at least one double bond, at least one triple bond, or at least one double bond and one triple bond. The hydrocarbon chain can be optionally substituted with one or more CM alkyl, C2.4 alkenyl, C2.4 alkynyl, CM alkoxy, hydroxyl, halo, amino, nitro, cyano, C3.5 cycloalkyl, 3-5 membered heterocycloalkyl, aryl, heteroaryl, CM alkylcarbonyloxy, Q-4 alkyloxycarbonyl, Ci-4 alkylcarbonyl, or formyl. The hydrocarbon chain can also be optionally interrupted by
-O-, -S-, -N(Ra)-, -N(Ra)-C(O)-O-, -O-C(O)-N(RaK -N(Ra)-C(O)-N(Rb>, -0-C(O)-O-, -P(R3)-, or -P(O)(R3)-. Each of Ra and Rb, independently, is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxylalkyl, hydroxyl, or haloalkyl. An aryl group is a substituted or unsubstituted cyclic aromatic group. Examples include phenyl, benzyl, naphthyl, tolyl, anthracyl, nitrophenyl, or halophenyl. A heteroaryl group is an aryl group with one or more heteroatoms in the ring, for instance furyl, pyiridyl, pyrrolyl, phenanthryl.
A suitable coordinating ligand can be purchased commercially or prepared by ordinary synthetic organic techniques, for example, as described in J. March, Advanced Organic Chemistry, which is incorporated herein by reference in its entirety. See also U.S. Patent Application No. 10/641,292 entitled "Stabilized Semiconductor Nanocrystals", filed 15 August 2003, which is hereby incorporated herein by reference in its entirety. See also other patents and patent applications referenced herein for additional descriptions of preparation methods.
Transmission electron microscopy (TEM) can provide information about the size, shape, and distribution of the nanocrystal population. Powder X-ray diffraction (XRD) patterns can provide the most complete information regarding the type and quality of the crystal structure of the nanocrystals. Estimates of size are also possible since particle diameter is inversely related, via the X-ray coherence length, to the peak width. For example, the diameter of the nanocrystal can be measured directly by transmission electron microscopy or estimated from X-ray diffraction data using, for example, the Scherrer equation. It also can be estimated from the UV/Vis absorption spectrum.
As discussed above, certain embodiments of a composition can include nanomaterial and a carrier medium (e.g., liquid, polymer, monomer, polymer or monomer solution, etc.). In certain embodiments, a carrier medium can be one in which the nanomaterial does not dissolve or does not appreciably dissolve (e.g., solubility is less than 0.001 mg/ml). In certain embodiments including a nanomaterial with one or more attached ligands, the carrier medium can be one in which the ligand not soluble or not appreciably soluble. In other embodiments, the medium can be one in which the ligand is at least partially soluble.
Examples of a liquid component for inclusion in compositions including nanomaterial (e.g, without limitation, semiconductor nanocrystals) include, without limitation, those listed in the following Table 1, and mixtures of two or more thereof. Examples of mixtures include hexane and octane; benzene and xylene; tetrahydrofurane and anisole; etc.
Table 1
Viscosity Relative Polarity
Liquid Formula @25°C Boiling Point (compared to
@1 atm water) cyclohexane C6Hi2 0.89 80.7 0.006 pentane CjH]2 0.24 36.1 0.009 hexane C6H |4 0.30 69 0.009 heptane C7H16 0.91 98 0.012 carbon tetrachloride CCl4 0.91 76.7 0.052
/7-xylene CβHio 0.63 138.3 0.074 toluene C7H8 0.56 1 10.6 0.099 benzene C6H6 0.60 80.1 0.1 1 1 diethyl ether C4H10O 0.22 34.6 0.117 methyl t- C5H12O 55.2 0.148 butyl alcohol dioxane C4H8O2 1.21 101.1 0.164 tetrahydrofurane C4H8O 0.47 66 0.207
(THF) ethyl acetate C4H8O2 77 0.228 d imethoxy-ethane C4H10O2 85 0.231
(glyme) diglyme C6H14O3 162 0.244 chloroform CHCl3 0.54 61.2 0.259 methylene chloride CH2CI2 0.43 39.8 0.309
2-butanone C4H8O 79.6 0.327 acetone C3H6O 0.31 56.2 0.355
/-butyl alcohol C4H10O 82.2 0.389 dimethyl-formamide C3H7NO 153 0.404
(DMF) dimethyl sulfoxide C2H6OS 189 0.444 (DMSO) acetonitrile C2H3N 0.35 81.6 0.46
2-propanol C3H8O 2.40 82.4 0.546
1 -butanol C4H10O 3.00 117.6 0.602
1 -propanol C3H8O 1.95 97 0.617 acetic acid C2H4O2 1 18 0.648 ethanol C2H6O 1.20 78.5 0.654 diethylene glycol C4H10O3 35.70 245 0.713 methanol CH4O 0.59 64.6 0.762 ethylene glycol C2H6O2 16.90 197 0.79 glycerin C3H8O3 1410.00 290 0.812 water, heavy (D2O) D2O 101.3 0.991 water H2O 1.00 100 1
Nonane (CH3(CH2)7CH 0.67 39.0
3)
Decane C|θH22 0.84 174.1
Dodecane C12H26 1.25 216.2
Chlorobenzene C6H5Cl 0.75 132
Dich lorobenzene C6H4CI2 174.0
Anisole C7H8O 0.92 154.0
Dimethyl formamide HCON(CH3)2 0.79 149.56 l-Methyl-2- 1.7 204.5 pyrrolidinone
Carbon tetrachloride CCl4 0.91 76.8
1,1,1 -Trichloroethane CH3CCl3 0.73 74.0
Tetrachloroethylene ClCH=CCl2 0.57 87.0
Ethylbenzene C8HiO 0.67 136.0
Other liquids or mixtures of liquids can be used. In certain embodiments, volatile liquids or mixtures of volatile liquids can be used.
In certain embodiments, a composition including nanomaterial and a liquid has a viscosity in a range of from about 0.1 centipoise (e.g., that of diethyl ether, methanol) to greater than 1500 centipoise (e.g., that of oils, glycerol). A composition including a nanomaterial and liquid may also be referred to as an ink. In embodiments including nanomaterial comprising semiconductor nanocrystals, a preferred liquid comprises an organic non-polar solvent. More preferably, such carrier has a viscosity less than or equal to about 1 cP and also relatively high volatility.
Optionally, other components can be included in the composition. Examples of other components that can be optionally included in the composition include, but are not limited to, e.g., surfactants, solvents, co-solvents, buffers, biocides, viscosity modifiers, complexing agents, chelating agents, stabilizing agents (e.g., to inhibit agglomeration of the nanomaterial), humectants etc. Other possible components include other additives of the type that may be included in ink or inkjet ink compositions. Stabilizing agents can include, e.g., chemically attached functional groups or ligands to form a coating around individual nanoparticles.
The amount (e.g., concentration (wt/vol)) of nanomaterial included in a composition can be selected based upon the particular nanomaterial and desired attributes of the deposited nanomaterial (e.g., thickness, optical density, features of the deposited nanomaterial (e.g., patterned or unpattemed, sizes of the features of a pattern, etc.)). The amount can be readily determined by a person of ordinary skill in the art.
For example, in certain embodiments of compositions including semiconductor nanocrystals and a carrier medium (including, e.g., but not limited to, a liquid comprising non-polar organic solvent or solvent mixture), the composition includes at least about 0.1 mg/ml semiconductor nanocrystals and/or composition. In examples of other embodiments, the composition can include at least 1 mg/ml, at least 5 mg/ml, at least 10 mg/ml, at least 25 mg/ml; at least 50 mg/ml, etc.
In certain preferred embodiments, the nanomaterial and any other optional solid components are dispersed in the composition when introduced onto the transfer surface. In certain preferred embodiments, the dispersion is colloidal.
A composition useful for depositing nanomateriai onto a substrate includes nanomaterial. The composition can further include a carrier medium (e.g., liquid, polymer, monomer, polymer or monomer solution, etc.). Optionally, the composition can further include one or more additional components. In certain embodiments, nanomaterial comprises nanoparticles. Examples of nanoparticles include, for example, a semiconductor nanocrystal, a nanotube (such as a single walled or multi-walled carbon nanotube), a nanowire, a nanorod, a dendrimer, organic nanocrystal, organic small molecule, other nano-scale or micro-scale material or mixtures thereof. Methods in accordance with the invention allow deposition of one or more nanomaterials and/or one or more compositions including nanomaterial onto a substrate. Such nanomaterial(s) and/or composition(s) can be deposited onto the substrate in a patterned or unpattemed arrangement.
Methods in accordance with the invention are particularly useful for applying one or more nanomaterials to a predefined region of a substrate, which may optionally include other materials, layers, components, and/or structures disposed thereon. As discussed above, nanomaterial can also be deposited with additional components included in a composition.
The predefined region is a region on the substrate where the nanomaterial can be selectively applied. The nanomaterial and surface can be chosen such that the nanomaterial remains substantially entirely within the predetermined area. Nanomaterial can be deposited onto the substrate such that the nanomaterial forms an unpattemed layer comprising nanomaterial within the predetermined area or a pattern comprising nanomaterial within the predetermined area. The pattern can be a regular pattern (such as an array, or a series of lines), or an irregular pattern.
Once one or more nanomaterials are deposited onto the substrate, the substrate can have a region including the nanomaterial (the predefined region) and a region substantially free of nanomaterial. In some circumstances, the one or more nanomaterials are deposited onto the substrate at a thickness of about a monolayer. In some circumstances, the thickness can be greater than a monolayer. The predefined region can be a discontinuous region. In other words, when the one or more nanomaterials are deposited onto the predefined region of the substrate, locations including nanomaterial can be separated by other locations that are substantially free of nanomaterial.
See, for example, A. Kumar and G. Whitesides, Applied Physics Letters, 63, 2002-2004, (1993); and V. Santhanam and R. P. Andres, Nano Letters, 4, 41-44, (2004), each of which is incorporated by reference in its entirety. See also U.S. Patent Application No. 11/253,612, filed 21 October 2005, entitled "Method And System For Transferring A Patterned Material", of Coe- Sullivan et al. and U.S. Patent Application No. 1 1/253,595, filed 21 October 2005, entitled "Light Emitting Device Including Semiconductor Nanocrystals," of Coe-Sullivan, each of which is incorporated herein by reference in its entirety.
When deposited in a patterned arrangement, nanomaterial can be deposited in a pattern comprising features having at least one dimension at a micron-scale (e.g., less than 1 mm, less than
500 μm, less than 200 μm, less than 100 μm or less, less than 50 μm or less, less than 20 μm or less, or less than 10 μm or less). Nanomaterial can also be deposited in a patterned arrangement comprising features at greater than micron-scale.
A pattern comprising deposited nanomaterial having features on the micron scale may also be referred to herein as a micropattern.
For example, a micropattern including 10-20 μm size features can be useful in light emitting device applications including, e.g., semiconductor nanocrystals.
The surface on which the nanomaterial can be deposited can have dimensions of 1 cm or greater, 10 cm or greater, 100 cm or greater, or 1,000 cm or greater.
Methods in accordance with the invention are scalable and can be useful in depositing a pattern comprising one or more nanomaterials over a wide range of surface areas.
For example, the method is useful for depositing nanomaterial over very small areas (for example, 100 μm catheters) to very large areas, (for example, 12" square areas). In further example, the method is also useful for depositing nanomaterial over surfaces with dimensions such as GEN2 (360 mm X 465 mm), GEN3 (550 mm X 650 mm), GEN3.5 (600 mm X 720 mm), GEN4 (730 mm X 920 mm), GEN5 ( 1110 mm X 1250 mm), GEN6 (1500 mm X 1800 mm), GEN7 (1900 mm X 2100 mm), and subsequent generations of glass that can be used, e.g., in displays. Optionally, areas onto which nanomaterial is applied can then be stitched (or tiled) together, to expand the printable area from 12" squares, to 'n x 12" squares' as is frequently done in the semiconductor lithography field.
In accordance with one aspect of the invention, a method for depositing nanomaterial onto a substrate comprises applying a composition comprising nanomaterial to a surface of a tape, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate.
As discussed above, in addition to nanomaterial, a composition can further include liquid or another carrier medium. Optionally, a composition can further include other components.
The nanomaterial applied to a surface of the tape can be patterned or unpatterned. A pattern can comprise an array of individual features at least one of which comprises nanomaterial. Typically, the individual features are spaced apart from each other. In certain embodiments, however, the features could be in contact with each other or even overlap.
In accordance with another aspect of the invention, there is provided a method for depositing nanomaterial onto a substrate. The method comprises applying a composition comprising nanomaterial to a surface of a tape from a transfer surface, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate. The nanomaterial applied to the substrate can be patterned or unpatterned
As discussed above, nanomaterial deposited by a method in accordance with the invention can include one or more nanomaterials, including, e.g., a mixture of two or more different nanomaterials. When nanomaterial is included in a composition, and two or more nanomaterials are to be deposited, different compositions including one or more different nanomaterials can be used.
If two or more different nanomaterials or mixtures of nanomaterials are to be deposited onto -a substrate, for example, the method can include applying different nanomaterials and/or mixtures of nanomaterials to a surface of a tape from a transfer surface in a single deposition step. In another embodiment, the method can include applying different compositions including different nanomaterials and/or mixtures of nanomaterials to a surface of a tape from a transfer surface in a single deposition step.
In another example, the method can include applying different nanomaterials and/or mixtures of nanomaterials to a surface of a tape from separate transfer surfaces in more than one deposition step. In another example, the method can include applying different compositions including different nanomaterials and/or mixtures of nanomaterials to a surface of a tape from separate transfer surfaces in more than one deposition step.
Other variations, including, for example, inclusion of optional additional steps are also contemplated.
If a composition includes liquid, in certain embodiments, all or substantially all of the liquid can be removed from the composition after the composition is applied to the tape. This allows the nanomaterial and any optional non-liquid components of a composition to be deposited onto the substrate by a dry (e.g., liquid-free or substantially liquid-free) transfer. A method including a dry transfer of nanomaterials onto the substrate can be advantageous when a liquid included in a composition can dissolve or otherwise react with the substrate.
A dry transfer process is preferred, for example, when transferring a composition including semiconductor nanocrystals from tape to an organic layer of a light-emitting device structure during device fabrication.
If interaction between the substrate and a liquid component is not a concern, the composition can be deposited onto the substrate without prior removal the liquid therefrom. The liquid can be removed after deposition of the composition(s) onto the substrate.
If a wet transfer is desired, and the liquid is appreciably volatile at ambient conditions, the time between application of composition(s) to the tape surface and deposition thereof onto the substrate is controlled to allow the deposition to occur while the composition(s) includes at least an amount of liquid.
In certain embodiments of the invention, a method of depositing one or more nanomaterials onto a substrate includes applying one or more liquid-free or substantially liquid-free nanomaterials to tape from a transfer surface; and depositing at least a portion of the nanomaterials from the tape onto the substrate.
This aspect of the invention can be particularly advantageous when depositing one or more nanomaterials onto a substrate in a predetermined pattern. By including a transfer of nanomaterial(s) from the transfer surface to the tape in the absence of a liquid component, blurring or distortion of patterned nanomaterial on the tape surface can be reduced. Such blurring or distortion can occur, for example, when the liquid including nanomaterial spreads on or wets the tape surface.
A transfer surface can be planar or contoured. A transfer surface can be rigid or flexible.
A transfer surface can be featureless or smooth (e.g. without elevations and/or depressions (e.g., grooves, recessed wells, etc.). A smooth transfer surface can be useful, for example, in a method for depositing an unpatterned layer onto a substrate. Examples of other embodiments including a smooth transfer surface are described below. A transfer surface can include one or more features (e.g., elevations and/or depressions (e.g., grooves, recessed wells, other three-dimensional features, etc.)). The arrangement of features can correspond to a predetermined pattern to be deposited onto a substrate. For example, in certain embodiments, a transfer surface including one or more depressions (e.g., grooves, recessed wells, other three-dimensional features, etc.) can be useful, for example, in a method for depositing a pattern comprising one or more nanomaterials onto a substrate. A transfer surface including elevated features can also be useful for depositing a pattern onto a substrate. For example, a composition including nanomaterial disposed on the elevated features of the transfer surface can be picked up with tape in the predetermined pattern and deposited onto the substrate.
A transfer surface can include a planar surface. A transfer surface can include a non-planar surface. In certain embodiments, a transfer surface can be curved.
Examples of transfer surfaces include, without limitation, a plate including a flat section of material (metallic, polymeric, silicon, for example), that can be smooth or include one or more depressions (e.g., a flat cliche) , a roller (e.g., with a circular, elliptical, or other rounded cross- section) including a predetermined pattern, a roller shaped transfer surface with a smooth surface (e.g., a roller shaped clichέ), etc.
One type of transfer surface useful in the present invention is known in the art as a cliche. Other types of transfer surfaces can also be readily identified and used.
In certain embodiments, a rigid transfer surface is preferred.
In certain embodiments, the transfer surface is made of polymer lined steel, thin (~1 mm) steel sheet or thick (~10 mm) steel plate. Other materials that can be used to fabricate a transfer surface include metal (e.g., aluminum, etc.) metal alloys, silicon, glass, ceramic, etc. Preferably, the transfer surface is fabricated from steel plate.
In embodiments of transfer surfaces including one or more grooves, the shape of the grooves can be rectangular or another geometric shape such as lines, square, triangular, circular, semi-circular, elliptical, semi-elliptical, other geometrical shapes, irregular shapes, customized shapes, etc. The grooves can have the same shape or may include any number of different combinations of geometrical, irregular, customized, etc. shapes, for example. The dimensions of a groove, for example, can optionally be on a micron scale (e.g., less than 1 mm, less than 500 μm, less than 200 μm, less than 100 μm, less than 50 μm, or 20 μm, 10 μm or less), or on a millimeter-scale or on a centimeter-scale or larger. Larger or smaller dimension grooves can also be used, depending on the predetermined pattern to be applied to substrate.
For example, the depth of a groove may be 0.01 μm (10 nm) to 100 μm, but is typically 25 μm in depth.
In embodiments of a transfer surface including two or more grooves, the grooves can be arranged in a pattern.
In embodiments of a transfer surface including depressions (e.g., grooves, recessed wells, other three-dimensional features etc.) arranged in a pattern, the size, shape, and arrangement of the patterned depressions in a transfer surface can be designed so as to correspond to a predetermined pattern to be deposited onto the substrate. The depth and contour of the depressions in the transfer surface are also designed to produce the predetermined pattern to be deposited onto the substrate.
For example, use of a transfer surface including a predetermined pattern of elevations or depressions (e.g., grooves, recessed wells, other three-dimensional features etc.) will permit the transfer of a predetermined pattern from the transfer surface to a surface of a tape. A pattern can be formed on a transfer surface by, for example, etching, general photolithography, or other known techniques in the relevant art.
FIG. 1 A illustrates a plan view of an example of a clichέ 100. As shown, a pattern of rectangular shaped grooves 102 is formed in the surface 104 of the cliche. Although the figure depicts rectangular shaped grooves, as discussed above, the shape, size, arrangement, depth, and contour of the grooves are selected based on the predetermined pattern to be deposited onto the substrate.
FIG. 1 B illustrates a plan view of another example of a cliche 100. As shown, the pattern of line-shaped grooves 102 is formed in the surface 104 of the cliche. The cliche includes a pattern of lines with different widths and different spacings. The figure contemplates that the clichέ grooves will be filled with three different colored compositions (e.g., red, green, and blue). Optionally, fewer or more different compositions can be included in the grooves. When a transfer surface includes a pattern of grooves, nanomaterial, and/or a composition including nanomaterial, can be introduced into one or more grooves in accordance with depositing the predetermined pattern including nanomaterial onto a substrate. The one or more nanomaterials or compositions can be included in at least a portion of a groove in accordance with the individual features of the predetermined pattern to be deposited on a substrate. As discussed above, the nanomaterial and/or composition included in the various grooves can be the same or different.
When a tape surface is contacted (e.g., by pressing) to the transfer surface and thereafter separated therefrom, the predetermined pattern including the composition(s) and/or nanomaterial(s) included in the grooves of the transfer surface, as the case may be, preferably becomes reversibly adhered to the tape surface. In certain embodiments, the predetermined patterned can thereafter deposited onto the substrate by contacting the nanomaterial disposed on the tape surface thereto.
As discussed above, in certain embodiments, a predetermined pattern can be deposited onto the substrate by including elevated features, corresponding to the predetermined pattern, on all or a portion of the transfer surface. In which embodiments, the nanomaterial disposed on the elevated features of the transfer surface can be picked up with a surface of a tape in the predetermined pattern and deposited onto the substrate by contacting the tape thereto.
In the various aspects of the invention, nanomaterial disposed on the transfer surface can be selectively removed in a predetermined pattern to be deposited onto the substrate.
For example, in certain embodiments, the transfer surface can be smooth or unpatterned. In such embodiments, one or more nanomaterials and/or one or more compositions comprising nanomaterial can be applied to the smooth transfer surface and applied to a tape surface as an unpatterned layer.
In certain other embodiments a pattern comprising one or more compositions or nanomaterials can be formed on the unpatterned transfer surface by, e.g., inkjet printing, silk- screening, other screen-printing technique, or other known technique for creating a pattern comprising one or more compositions or nanomaterials on the smooth transfer surface. A pattern formed on a transfer surface in such manner corresponds to the predetermined pattern including one or more nanomaterials to be deposited onto the substrate. In another aspect of the invention, for example, a predetermined pattern can be formed on a transfer surface with use of a mask including one or more apertures. The number, size, shape, and arrangement of the apertures will be selected based on the predetermined pattern that is desired.
In certain embodiments, an example of which is depicted in FIG. 2 A, for example, a mask including one or more apertures corresponding to the predetermined pattern can be placed on the transfer surface before the nanomaterial and/or composition is to be picked up by a surface of a tape. In such case, the tape surface, preferably unfeatured, can pick up the nanomaterial and/or composition including nanomaterial from the transfer surface through the apertures arranged in a predetermined pattern to form patterned nanomaterial and/or composition thereon. The tape surface including the patterned nanomaterial and/or composition can thereafter be contacted to the substrate to deposit the pattern thereon. The nanomaterial and/or composition is preferably introduced to the transfer surface prior to positioning the mask thereon. In certain embodiments, any liquid is preferably removed from the nanomaterial and/or composition prior to positioning of the mask on the transfer surface.
In certain other embodiments (not shown), nanomaterial and/or a composition including nanomaterial is deposited onto the transfer surface through a mask including one or more apertures arranged in the predetermined pattern. After the mask is removed, the patterned nanomaterial deposited onto transfer surface through the apertures can be picked up by a surface of a tape, preferably with an unfeatured surface. The nanomaterial can thereafter be deposited onto the substrate from the tape surface.
In certain preferred embodiments, an example of which is depicted in FIG. 2 B, a predetermined pattern can be formed on a substrate by positioning a mask including one or more apertures arranged in a desired predetermined pattern on the substrate prior to contacting the tape surface including nanomaterial to the substrate. By contacting the tape surface including the nanomaterial and/or composition to be applied to the substrate through the mask apertures, a pattern of the nanomaterial and/or composition is applied to the substrate. In certain embodiments, the nanomaterial and/or composition on the tape surface is preferably dry (e.g., at least substantially free of liquid) prior contacting the tape surface to the substrate through the mask apertures. In certain embodiments, nanomaterial may be deposited through less than all of the apertures. In certain embodiments, the nanomaterial and/or composition on the tape surface preferably comprises an unpatterned layer. In certain embodiments involving printing of nanomaterial (preferably semiconductor nanocrystals) and/or compositions including nanomaterials (preferably semiconductor nanocrystals) in hybrid inorganic-organic devices, the deposition (also referred to herein as printing) step(s) are preferably carried out in a nitrogen or vacuum environment.
In certain embodiments, a mask can be fabricated from a class of films comprising polyimides including fluorinated polyimide films or film coated, at least on one side, with a fluorinated material. In certain embodiment, a film coated, on at least one side, with a coating comprising an aromatic material. In certain embodiments, one side of the film can be coated with a fluorinated material and the other side can be coated with an aromatic material.
In certain embodiments in which a side of the mask is positioned on the substrate, it is preferred to use a fluorinated polyimide film or film coated, at least on one side, with a fluorinated material, with the side of the film including the fluorinated material being positioned against the substrate.
In certain embodiment, if a mask comprises plastic and/or a plastic coating, it is preferably baked out at elevated temperature with vacuum to remove VOCs, etc. prior to printing.
Masks of different thickness can be used. By way of non-limiting example, a mask comprising a polyimide film having a thickness of 1 mil polyimide can be used. Thinner and/or thicker masks are also suitable. Masks thinner than O.S mil are desirable for printing higher resolution patterns. Masks with a thickness less than 0.5 mil may require tensioning. Alternatively, the rigidity and/or dimensional stability of masks with a thickness less than O.S mil can be enforce with a thin steel foil. In certain other embodiments, a mask can comprise a rigid foil which optionally can be coated on one or both sides with a soft coating (e.g, Teflon).
A mask can be patterned with a predetermined pattern by known techniques (including, but not limited to, photo-etching and laser patterning) or unpatterned.
Examples of film materials from which a mask can be made include, without limitation, polyimide films such as, for example, and without limitation, 6FDA-ODA Fluorinated Polyimide, 6FDA-PMDA Fluorinated Co-Polyimide, 6FXDA-6FDA Fluorinated Polyimide Foam, Amoco Ultradel 4212 HFDA-APBP Polyimide, Au/Cr/Polyimide Composite, BPDA-ODA Polyimide, BPDA-PDA Polyimide Film, BPDA-PFMB Polyimide, BTDA-APB Polyimide, BTDA-ODA Polyimide, BTDA-PDA Polyimide, Ciba-Geigy Probimide 348 PMDA-ODA Polyimide, Ciba- Geigy Probimide 412 PSPI, Ciba-Geigy Probimide 414 PSPI, Ciba-Geigy XU-287 Soluble
Polyimide, Cu/Cr/BPDA-PDA Polyimide Composite, Cu/Cr/PMDA-ODA Polyimide Composite, DuPont 5810D BPDA-PDA Polyimide, DuPont 5879HP PMDA-ODA Polyimide, DuPont FPI- 136M Fluorinated Polyimide, DuPont FPI-45M FIuorinated Polyimide, DuPont Kapton 100 HN Polyimide Film, DuPont Kapton 300H Polyimide Film, DuPont Kapton 500HN Polyimide Film, DuPont Kapton Type H Polyimide Film, DuPont Kapton Type HN Polyimide Film, DuPont PI-2540 PMDA-4,4'-ODA Polyimide, DuPont PI-2545 PMDA-ODA Polyimide, DuPont PI-2556 BTDA- ODA-MPD Polyimide, DuPont PI-2560 BTDA-MPD-ODA Polyimide, DuPont PI-5878 PMDA- ODA Polyimide, DuPont Pyralin PI-261 1 BPDA-PDA Polyimide, DuPont Pyralux Polyimide, GE Ultem Polyetherimide, Hitachi PIQ LlOO Polyimide, Hitachi PIX LI lO Polyimide, Mitsui Toatsu Aurum 450C Thermoplastic Polyimide, OMM Probimide 1 12A, OMM Probimide 114A, OMM Probimide 115A, OMM Probimide 1 16A3 OMM Probimide 7005, OMM Probimide 7010, OMM Probimide 7020, OMM Probimide 7505 PSPI, OMM Probimide 7510 PSPI, OMM Probimide 7520 PSPI, PMDA-3,4'-ODA Polyimide, PMDA-3FDA Fluorinated Polyimide, PMDA-3FDA Fluorinated Polyimide Foam, PMDA-ODA Polyimide, PMDA-ODA m-diethylester, PMDA-PDA Polyimide Film, Probimide 32 Polyamide-imide, SE45 Siloxane - Polyimide, Upilex R Polyimide Film, and Upilex S Polyimide Film.
Optionally, a mask can further include a hole in each of the four corners to mount and tension a mask to a rigid frame, which is preferred with thin masks, as discussed above. Various known techniques can be used to align a series of masks to be used to print and register multiple nanomaterials on a single substrate.
In certain embodiments, the mask can be placed against the transfer surface or substrate without gaps in between the transfer surface or substrate, as the case may be, and the underside of the mask.
One or more nanomaterials or compositions can be transferred from the transfer surface to tape surface by, for example, contacting (e.g., pressing) the tape surface against the transfer surface including the one or more compositions or nanomaterials to be deposited.
The one or more compositions or nanomaterials transferred to the tape surface from the transfer surface preferably become reversibly adhered to the tape surface for later deposition onto the substrate.
As discussed above, in certain embodiments, the one or more compositions can thereafter be deposited from the tape surface onto the substrate. If a wet transfer of composition(s) onto the substrate is desired, the time between patterning the tape surface and depositing the pattern onto the substrate is minimized to allow the pattern to transfer while the patterned nanomaterial still includes at least an amount of the liquid.
As also discussed above, in certain other embodiments, the liquid can be removed from composition(s) by, for example, evaporation, before the remainder of the composition (e.g., nanomaterial and any other optional components) is deposited on the substrate.
Certain other embodiments include a dual dry transfer. A dual dry transfer includes a liquid- free or substantially liquid-free transfer of one or more nanomaterials from the transfer surface to the tape surface and a liquid-free or substantially liquid-free transfer or the one or more nanomaterials from the tape surface onto the substrate. A substantially liquid-free transfer includes, for example, no more than about 10 parts per hundred liquid, preferably no more than about 10 parts per thousand liquid, and more preferably no more than about 10 parts per million liquid.
For example, when one or more nanomaterials are introduced to a transfer surface as a component of a composition that also includes liquid, one or more nanomaterials can be transferred from the transfer surface to a tape surface by, for example, contacting the tape surface against the transfer surface after the liquid is removed from the composition. The liquid can be removed, for example, by evaporation at ambient conditions, by application or heat to accelerate evaporation, by adjusting the pressure to accelerate evaporation, by modifying the temperature and pressure to accelerate evaporation, etc.
The one or more nanomaterials transferred to a tape surface from the transfer surface preferably become reversibly adhered to the tape surface upon contacting the tape surface to the transfer surface. The one or more nanomaterials can thereafter be deposited from the tape surface onto the substrate.
As discussed above, a dry transfer process of one or more materials from the tape surface onto the substrate can be advantageous when the liquid of the composition(s) including the nanomaterial(s) can dissolve or otherwise react with the surface of the substrate. Employing a dry transfer of nanomaterial(s) from the tape surface onto the substrate frees the substrate of solubility and surface chemistry requirements.
A dual dry transfer can also be used to deposit unpatterned layers comprising nanomaterial. Methods in accordance with the invention can be used to deposit a pattern comprising two or more different nanomaterials onto a substrate. The two or more different nanomaterials can be deposited sequentially or in a single step.
For example, each of the two or more different compositions or nanomaterials can be deposited in sequential separate depositions steps. This embodiment can be used, for example, when depositing a pattern comprising different color compositions or nanomaterials, and each color is deposited onto the substrate separately.
Preferably, each transfer is aligned and registered so that the predetermined pattern is deposited onto the substrate at a predefined location.
The method is compatible with various well-known alignment and registration techniques for example, when more than one pattern is deposited onto the substrate in more than one transfer. Factors that can affect the registration of subsequent printing steps onto a single substrate include multiple well pattern (e.g., groove) offset, as well as the travel distance from one nanomaterial deposition to the next. Since both of these parameters can be tuned on the micron scale, high repeatability after tuning is expected.
In certain embodiments, two or more different compositions or nanomaterials are deposited by a single transfer step. This can be achieved with use of a transfer surface which includes the two or more different compositions or nanomaterials on the surface thereof. For example, the two or more nanomaterials can be included in the grooves of a single transfer surface for simultaneous transfer. Alternatively, the two or more nanomaterials can by patterned on an smooth transfer surface by, e.g., inkjet or silk-screen printing, other screen-printing technique, vapor deposition (e.g., including masks to form a pattern comprising nanomaterials). In a further embodiment, each composition or nanomaterial can be applied to the same tape surface one at a time in separate application steps to provide the predetermined arrangement of nanomaterials thereon.
When two or more nanomaterials, or two or more compositions, are transferred in the desired arrangement from a transfer surface by a single transfer step, the lateral offset of the patterns of the different nanomaterials, or compositions, can be better-controlled than when each of the different nanomaterials or compositions are transferred separately. This can reduce or preferably eliminate variation from printing to printing. Expected registration accuracy and repeatability can be better than lOOμm, as good as lμm, and eventually as good as IOnm with precise mechanical systems. For example, the transfer surface can include a predetermined arrangement of different compositions that include semiconductor nanocrystals that emit light at different wavelengths. By including such arrangement of semiconductor nanocrystals that emit light at different wavelengths, a multicolor pattern can be formed on a tape surface for deposition onto the substrate.
Embodiments of the invention can also optionally include transferring more than one layer simultaneously, for example a blanket deposited (unpatterned) layer of a first material (e.g., metal, metal oxide, etc.) can be applied to a surface of a tape and a patterned second material (e.g., semiconductor nanocrystals, etc.) applied thereto. Upon contacting the tape surface to the substrate, the patterned second material is transferred as well as the blanket of first material.
Depending upon the nature of the nanomaterial and/or composition comprising nanomaterial being used, the nature of the substrate, and/or the end-uses for an article or device including the deposited composition or nanomaterial, it may also be desirable to carry out the method in a controlled environment, e.g., in a hood, glove box, under an inert atmosphere, under nitrogen, etc.
In certain embodiments, the transfer surface can be treated (e.g., by application of one or more coatings) or otherwise surface modified (e.g., chemical modification of the surface, energetic treatments (including, but not limited to, plasma treatment, laser treatment, etc.), or other suitable surface-modification techniques). A surface treatment can be applied to all or one or more portions of the surface. A surface treatment of the transfer surface can be included whether the surface is featureless or whether the surface includes features (e.g., one or more grooves). A surface treatment can include different treatments to different areas of the transfer surface. For example, the grooves (e.g., the side walls and trough of the grooves) can receive one type of surface treatment, and the top transfer surface (between the grooves) can receive a different type of surface treatment. The treatments can be applied, for example, to alter the properties (e.g., wetting attributes) of the transfer surface or portions thereof. For example, depending upon the wetting attributes of the composition and the wetting attributes of the non-grooved surface of the transfer surface and/or the surface of the grooves, it may be desirable to alter the surface energy of the non-grooved transfer surface and/or the surface energy of one or more of the grooves. Such surface energy modifications can be made, for example, by including a coating on the surface of the grooves of the transfer surface, on the non- grooved portion of the transfer surface, or both. Optionally, a first coating is applied to the surface of the grooves and a second coating is applied to the rest of the transfer surface, each coating material having either hydrophilic or hydrophobic properties, selected to reduce spreading. Examples of various surface treatments that can be applied to the transfer surface include trichlorosilanes, other silylation treatments, teflon, etc. Selection of other surface treatments can be readily made by those of ordinary skill in the relevant art. In certain embodiments, silanized transfer surfaces can be preferred.
In certain embodiments, the surface energy of the groove surface can be modified to enhance wettability of the groove surface so that the composition dispensed in the groove spreads within the groove.
Preferably, the surface energy of the non-grooved surface of the transfer surface is modified to decrease the wettability so that the spreading of the composition on the non-grooved transfer surface is reduced, and preferably prevented. Modification of the non-grooved transfer surface can reduce the transfer of pattern defects that can result from the spread or other occurrence^) of composition or nanomaterial on the non-grooved transfer surface at or prior to transfer of the composition from the groove(s) to the tape. Modification of the grooves can facilitate the spread of the composition within the entire groove to assist pick-up of the full groove shape and size.
Preferably, a tape has a predetermined dimension so that a pattern can be formed by one time transfer, even, for example, in case of a display device having a large area by using an tape having dimensions corresponding to a selected area of the display device.
The tape preferably has a configuration and dimensions selected for picking up the pattern formed from the filled transfer surface grooves.
The tape can be configured to move or be moved relative to the position of other components of the printing system being used, e.g., the transfer surface and/or the uppermost surface of the substrate on which a nanomaterial or composition is to be applied. The surface of the tape can include an elevation or a depression, or the tape can be substantially free of elevations and/or depressions.
In certain embodiments, the surface of a tape to which nanomaterial is to be applied can be smooth or featureless (e.g., an absence of elevations and/or depressions of a pattern). In certain other embodiments, it can be patterned (e.g., featured).
Optionally, a surface chemistry layer can be disposed over the surface of a tape to which nanomaterial is to be applied. A surface chemistry layer can be applied by physical vapor deposition (PVD), chemical vapor deposition (CVD) , or liquid or gas phase coating by a self- assembled monolayer, depending on the desired material surface properties.
The composition of the surface chemistry layer can be selected to readily adhere and release a composition including nanomaterial , in a wet transfer, or nanomaterial, in a dry transfer. The surface chemistry layer can optionally act as an adhesion/surface chemistry layer for the composition or nanomaterial. Aromatic organic polymers, deposited by chemical vapor deposition, can be used as a surface chemistry layer. See, for example, S. Coe-Sullivan, et al., Advanced Functional Materials, 15, 1 1 17-1 124 (2005), which is incorporated by reference in its entirety. The surface chemistry layer can be chosen to compatible with spreading of the composition which includes nanomaterial and a liquid. For example, with a liquid comprising chloroform, the surface chemistry layer can be a chemical vapor deposited Parylene-C layer or other surface chemistry material.
In certain embodiments, a surface chemistry layer comprising Parylene-C can be included on a surface of tape to assist complete release of the nanomaterial from the surface thereof. For example, a surface chemistry layer comprising Parylene-C is compatible with a wide range of liquids (e.g., non-polar organic liquids). Parylene-C is an aromatic polymer that can form thin and conformal coatings exhibiting highly inert properties.
The above properties of Parylene-C make it a suitable surface chemistry layer for use in depositing nanomaterials comprising semiconductor nanocrystals, particularly when deposited in thin layers including same. Optionally, a surface chemistry layer can include different parylene compositions or other surface chemistry materials (e.g., but not limited to, surface modifying organic molecules, plastics, and other surface chemistry treatments known or identifiable by a skilled artisan in the relevant art for achieving the desired surface properties). Other parylene materials that could be used in a surface chemistry layer include, for example, but are not limited to, Parylene, Parylene-N, Parylene-F, Parylene-D, Parylene-HT, Parylene AF4, etc. In certain embodiments, other surface treatments (e.g., energetic treatments including, but not limited to, plasma treatment, laser treatment, etc.) known or recognized in the art can be used.
In certain circumstances, a surface chemistry layer comprising Parylene-C may undergo as least partial delamination from PDMS. The can occur for example, due to temperature effects (in light of the differences between the thermal coefficients of the two materials) and/or upon repeated application of pressure. Such delamination problems can be reduced or avoided with use of surface chemistry release layer comprising organic molecular compounds. Such compounds can be included in a surface coating on a tape surface. Preferably the surface coating has a surface energy less than about 50 mJ/m2, more preferably less than about 30 mJ/m2, and most preferably less than about 20 mJ/m2. In certain embodiments, the organic molecular compounds can be aromatic molecular compounds. In other embodiments, the surface chemistry layer comprises xxx-silanes. Such materials include functional groups that can bond with functional groups at the elastomer surface and self-align themselves on the surface forming an organized coating. It is expected that these materials will remain immune to the dimensional changes in the elastomer originating from temperature variations or mechanical impact, and would maintain its de-wetting function over extended period of time. Examples of organic molecular compounds for inclusion in a surface chemistry release layer include, but are not limited to, aromatic organic molecular compounds.
Other examples of compounds for inclusion in a surface chemistry release layer include, but are not limited to, ethyltrichlorosilane, ethyltriethoxysilane, n-propyltrichlorosilane, n- propyltrimethoxysilane, n-butyltrichlorosilane, n-butyltrimethoxysilane, n-hexyltrichlorosilane, n- hexyltrimethoxysilane, n-octyltrichlorosilane, n-octyltriethoxysilane, n-decyltrichlorosilane, n- dodecyltrichlorosilane, n-dodecyltriethoxysilane, n-octadecyltrichlorosilane, n- octadecyltriethoxysilane, n-octadecyltrimethoxysilane, water soluble octadecylsilane, n- exosyltrichlorosilane, n-docosyltrichlorosilane, phenyltrichlorosilahe, phenyltriethoxysilane, (tridecafluoro- 1 , 1 ,2,2-tetrahydrooctyl)- 1 -trichlorosilane, and (tridecafluoro- 1 , 1 ,2,2-tetrahydrooctyl)- 1 triethoxysilane. In certain embodiments, the compounds can be hydrophobic.
In certain embodiments, the tape surface is contacted to the surface of the substrate under conditions to cause at least a portion of the nanomaterial included on the tape to be deposited onto the substrate For example, in certain embodiments, the tape can be contacted to the substrate at a pressure of at least 0.1 lb/in2 for at least a period of time effective for transferring at least a portion of the nanomaterial onto the substrate, e.g., thirty seconds or less. In certain embodiments, for example, the pressure is at least 1 lb/in2', but less than 50 Ib/ in2. In certain other embodiments, for example, the pressure is in the range from about 100 Ib/ in2 to about 500 Ib/ in2 In certain other embodiments the pressure is less than the pressure at which the film or substrate is damaged.
One or more compositions including one or more nanomaterials can be delivered to a transfer surface by various techniques. For example, the composition(s) can be dispensed from an inkcup, a micro-dispenser (e.g., a needle, inkjet print head, nozzles, syringe, etc.), an array of micro-dispensers (e.g., an array of needles, an array of multiple inkjet heads, an array of nozzles, misters, and array or syringes, etc.) that are movably mounted to be positioned over and aligned with the location on the transfer surface to which one or more compositions are to be dispensed. Preferably, a predetermined metered amount of a composition is dispensed. Techniques for delivering or dispensing composition to a transfer surface will be discussed further below. Optionally, various masking techniques can be further included with techniques for delivering or dispensing a compositions selectively to a transfer surface.
For example, one or more compositions can be dispensed to one or more grooves of the transfer surface by various techniques, including, but not limited to, use of an inkcup or from a micro-dispenser or an array of micro-dispensers (e.g., needles, inkjet nozzles, misters, etc.) positioned over and aligned to dispense a metered amount of composition into each groove to be filled.
An inkcup technique can be particularly useful for dispensing the composition into transfer surface grooves. Any type of inkcup can be used, for example, an open inkcup, a closed inkcup, or a pressurized inkcup.
In an open inkcup, the content is confined in a well that is open to the atmosphere. Depending on the properties of the content, the content of an open inkcup can experience variations in concentration and viscosity caused by evaporation. Such variations can affect the quality of the pattern of nanomaterial that is deposited onto the substrate.
In a closed inkcup, the content is confined in a well that is closed to the atmosphere, so variations to the content that can result from evaporation are reduced or eliminated. For this and other reasons, a closed inkcup is preferred. A closed inkcup can be positioned upside down and slide over the transfer surface or the transfer surface may slide over the inking surface of the inkcup. The latter approach requires the inkcup to be pressurized. A pressurized inkcup typically includes a diaphragm that supports the ink well and can be raised to wet the transfer surface pattern and then retracted.
The pressurized ink cup can be particularly useful when printing has to be done on the surfaces that are not horizontally positioned relative to the inking surface of the inkcup.
With a closed inkcup system, the composition to be dispensed is confined within the inkcup. The edge of the inkcup that is in contact with the transfer surface during the dispensing of the composition is sometimes referred to as a doctor ring. This edge in contact with the transfer surface forms a seal with the transfer surface. In certain embodiments, the seal can be improved by application of pressure. The seal between the inkcup edge and the transfer surface depends upon the flatness of these parts and also on surface finish of each. When an inkcup is used to dispense the composition, the area of the transfer surface containing the grooved pattern is preferably planar and preferably smooth.
The sealing force between the ink-cup and surface of the transfer surface is also dependent on the mass of the inkcup and any additional pressure applied to the inkcup when contacted to the transfer surface. Optionally, the seal between the inkcup and surface of the transfer surface can be further reinforced by, for example, a magnetic force originated by magnets located within the body of the ink-cup and under transfer surface that is magnetic, e.g., a steel plate.
Inkcups can be used with compositions of having viscosities, for example, from greater than about 1 cP to about 20 cP, less than about 1 cP, greater than about 2OcP, etc.
The edge of the inkcup that is in contact with the transfer surface acts as a doctor blade. When the inkcup is moved across the transfer surface, the composition is filled into the grooves over which the inkcup is moved, and the composition which remains at the surface of the transfer surface between the grooves is removed. The use of an inkcup allows for a high degree of flexibility and control over how to introduce the composition to the inkcup.
Manipulation of pressure (e.g., by vacuum (e.g., within the inkcup) or positive pressure) allows the control of leakage of low viscosity inks from the transfer surface/inkcup assembly, as well as control of concentration variations that could be associated with any such leakage.
When two or more different compositions are to be dispensed into certain transfer surface grooves, they are preferably dispensed from an inkcup one composition at a time.
Preferably, a tight seal is maintained between the portion of the inkcup (e.g., doctor ring) in contact with the transfer surface and the transfer surface itself to confine the composition within the cup. This can be particularly useful when the composition includes a carrier medium having a low viscosity liquid. More preferably, the portion of the inkcup in contact with the transfer surface comprises a substantially smooth, planar finish.
Optionally, the surface energy of the portion of the inkcup in contact with the transfer surface can be modified to increase the dewetting characteristics thereof with respect to the composition being dispensed by the inkcup. Such modification of the inkcup can assist in reducing the possibility of leakage of the composition through any surface imperfections at the seal between the inkcup and the transfer surface so that the composition preferably remains confined within the cup when moving across the transfer surface until deposited in the grooves of the transfer surface pattern.
The surface modification of the inkcup edge can optionally be utilized with one or more surface energy modifications of the transfer surface(s) discussed above. It is believed that any such surface modifications, alone or in combination, can extend the range of liquid viscosity to lower values, and improve uniformity of transferred patterns.
Most preferably, the mating seal counterparts, the doctor ring, and transfer surface are free of surface defects such as cracks, grooves, indentions, or even micro scale damage to prevent leakage of the composition.
The edge of the inkcup in contact with the transfer surface and/or the non-grooved surface of the transfer surface are optionally planarized and/or polished to reduce, and preferably, eliminate defects that can result in leakage of composition from the mated surfaces while the composition is being dispensed into the grooves.
Optionally, these two surfaces comprise materials with different hardnesses, such as, for example, a cliche comprising steel and an inkcup with an edge comprising a ceramic material that is softer than the steel used to fabricate the cliche. Various other materials of construction and/or their combinations, such as various ceramics, ceramic coating, glass, metals, or silicon may alternatively be utilized, for the transfer surface and inkcup edge.
An inkcup can be used in a static fashion, where the cup is filled, sealed, and not tampered with through successive prints. Alternatively, a flow system can optionally be utilized to reflow the composition from the inkcup to a reservoir, thereby maintaining and stabilizing the composition concentration and viscosity. The composition in a reflow loop may further optionally be monitored for concentration (via various optical means, for example) and the concentration maintained actively by addition of controlled quantities of carrier medium or concentrated composition or nanomaterial into the reflow loop to lower or raise the concentration of nanomaterial in the composition.
Another technique that is particularly useful for dispensing one or more compositions (e.g., different colored compositions) onto a transfer surface includes use of a micro-dispenser or an array of micro-dispensers (e.g., needles, inkjet nozzles, etc.) positioned over and aligned to dispense such composition or compositions thereto. In certain embodiments, the transfer surface includes one or more depressions (e.g., grooves, recessed wells, etc.), in which case, the micro-dispenser or array of micro-dispenses can be aligned to deliver the composition(s) into the individual grooves. Such micro-dispensers can optionally deliver different compositions to the transfer surface simultaneously or sequentially.
When the composition is dispensed from one or more micro-dispensers to grooves of a transfer surface, the transfer surface grooves can be filled by moving the transfer surface relative to the micro-dispenser(s) or alternatively, the micro-dispenser(s) can be moved relative to the grooves of the transfer surface, with the moving component being stopped at intervals selected to permit filling of unfilled grooves until all of the grooves are Tilled.
A micro-dispenser can be used to fill each of the grooves with the same composition. Two or more different compositions can be dispensed into the transfer surface grooves by sequential delivery of each composition from a micro-dispenser. Two or more different compositions can be dispensed into the transfer surface grooves non-sequentially. For example, an array of multiple micro-dispensers, e.g., an ink jet system having multiple print heads, can dispense different nanomaterials in a non-sequential manner. An array of micro-dispensers can also be programmed to dispense compositions into the grooves sequentially or in accordance with another predetermined order based on the pattern, groove location, dimensions of the transfer surface, etc.
FIG. 3 depicts a schematic of an example of a system including an array of micro-dispensers for dispensing one or more compositions into grooves of a cliche: The cliche 450 includes a predetermined pattern of grooves in the upper surface 455 thereof. An array micro-dispensers 410 is disposed over the cliche to dispense compositions into the grooves. At dispensing time, each micro-dispenser is aligned with the groove into which a given composition is to be dispensed.
FIG. 4 depicts a schematic of example of a system for dispensing more than one composition into grooves of a cliche. The system includes an array of micro-dispensers that are spatially arranged for dispensing compositions into the predetermined pattern formed by the array of grooves on the transfer surface. Optionally, micro-dispensers can be positioned along a dimension (e.g., length, width, diagonal, etc.) of the cliche. Optionally, the individual micro-dispensers of an array can be arranged in a linear arrangement, but the arrays are positioned above the transfer surface at an angle to allow dispensing compositions into closely spaced grooves. Alternatively, a linear array of micro-dispensers are positioned above transfer surfaces that are disposed on an angle. Other configurations of the transfer surface grooves and the array of micro-dispensers are possible.
The relative placement of the micro-dispensers corresponds to the pattern of the clichέ so that when a composition is dispensed into a groove, the dispensed composition will spread in or wet a groove of the cliche due to surface tension and gravity. Subsequent to filling a groove, the micro-dispenser can be moved to be positioned over the next groove to receive the same composition. The micro- dispenser array will continue to move over the area of the pattern dispensing the composition in a continuous mode or by multiple injections. A second micro-dispenser array will similarly dispense a second composition into the appropriate grooves in accordance with the predetermined pattern.
After the grooves are filled with the one or more different compositions (e.g., three different compositions, each respectively comprising, e.g., blue-emitting, green-emitting, and red-emitting semiconductor nanocrystals (also referred to as quantum dots (abbreviated as "QD" in FIG. 4)), the predetermined pattern is transferred to a tape surface and the pattern can thereafter be applied to the substrate.
Preferably, one or more compositions or nanomaterials are deposited onto a substrate in a single deposition step. This single transfer process reduces and preferably eliminates variations in the concentrations of nanomaterial in the composition during the deposition of the pattern to the substrate.
The use of a single deposition step to transfer a complete pattern or multiple components of a pattern avoids the need to register subsequent stamps to the previously deposited patterns. Further, by reducing the number of instances of contact between the tape and the substrate to which nanomaterial has been previously applied, the possible damage to, or disruption of, the previously applied nanomaterial is reduced. For example, in depositing a pattern comprising different color nanomaterials comprising semiconductor nanocrystals to a substrate, a single step transfer reduces the risk of damage to the patterned nanomaterials. This can be particularly advantageous when the nanomaterials are applied in thicknesses of several monolayers or less.
In certain embodiments, multiple compositions can be dispensed from micro-dispensers disposed over the transfer surface in an array. Each of the micro-dispensers can dispense a composition at the same or different times. Optionally, the transfer surface can be moved under a positioned dispenser or micro-dispenser array, the dispenser or micro-dispenser can be moved over a positioned transfer surface, or the transfer surface and array can each be moved into alignment at or prior to the time the grooves are filled. To transfer a pattern comprising different nanomaterials in a single transfer step, all of the various compositions including the different nanomaterials to be deposited are dispensed into the patterned grooves before the tape is contacted to the transfer surface.
If a dry transfer is desired, for example, the transfer surface is not contacted to the substrate until any liquid component of the composition(s) evaporates from the transfer surface, leaving liquid-free, or substantially liquid-free, nanomaterials on the transfer surface. As discussed above, a substantially liquid-free transfer includes, for example, no more than about 10 parts per hundred liquid, preferably no more than about 10 parts per thousand liquid, and more preferably no more than about 10 parts per million liquid.
By depositing more than one nanomaterial onto the substrate in a single transfer, better control of the concentration of the composition can be possible. Additionally, cleaning steps between separate transfers of different nanomaterials can be avoided.
As discussed herein, the ability to transfer a pattern comprising more than one nanomaterial by a single transfer further avoids the need to register the alignment of successive transfers of separate transfers of each individual nanomaterial and eliminates the need to index successive transfers of each individual nanomaterial. Scaie-up can also be facilitated.
Another technique for depositing a pattern comprising nanomaterial onto a substrate includes the use of a tape. The tape can act as a donor surface for depositing nanomaterial onto a substrate or onto a temporary transfer surface. FIG. 5 depicts the relative arrangement of a tape and substrate to receive the deposited composition(s) or nanomaterial(s). In the example shown, the tape is contacted to the substrate with use of a presser (depicted in the illustrated example as a stamp). In the example shown in FIG. S the presser comprises a roller with a circular cross-section. Alternatively, a roller with an oval cross section, a stamp, or other device suitable for depressing the tape against the transfer surface and/or substrate may optionally be used.
Other techniques, methods and applications that may be useful with a tape including nanomaterial disposed thereon are described in U.S. Provisional Patent Application No. 60/790,393, entitled "Methods And Articles Including Nanomaterial", of Seth Coe-Sullivan, Maria J. Anc, LeeAnn Kim, Vladimir Bulovic, Ioannis Kymissis, John E. Ritter, and Robert Praino, filed by Express Mail on 7 April 2006, the disclosure of which is hereby incorporated herein by reference in its entirety. FIG. 7 provides a schematic example of a system including a tape for depositing nanomaterial onto a substrate.
Referring to FIG. 7, the deposition of one or more nanomaterials onto a substrate is facilitated by pick up of a composition comprising nanomaterial, unpatterned or in a predetermined pattern, from a transfer surface (e.g., a cliche system as depicted) onto a surface of the tape 92 which is run through the system. The nanomaterial is subsequently transferred to the substrate 98. A presser 94 (examples of which include a roller (having e.g., circular or oval cross-section) or a stamp (examples of which are depicted in FIG. 6) or other suitable component may be used to press the tape against the transfer surface and/or to press the tape against the substrate. The presser and tape act as an applicator to deposit nanomaterial onto the substrate.
Optionally, the tape and presser can be selected to have dimensions selected such that the substrate can be fully patterned in a single process step.
The tape can optionally be a consumable or can be recycled. If recycled, the tape will preferable be clean before being reused. Optionally, this method can carried out in a continuous manner (e.g., roll to roll).
As discussed above, a tape can optionally further include a release layer or other surface treatment of the tape surface, tape dispensing components, post-use conditioning of the tape (dry or wet cleaning), etc.
In embodiments including deposition of a predetermined pattern comprising one or more different nanomaterials, the number, arrangement, shape, and size of the grooves of the transfer surface and the nanomaterials included therein will be selected according to the predetermined pattern to be deposited onto the substrate. The one or more compositions comprising the nanomaterials to be deposited can be dispensed into the grooves by any of the above-discussed techniques or other suitable techniques for dispense compositions and/or nanomaterials onto a transfer surface.
The use of a tape to deposit nanomaterial onto the substrate is expected to deposit nanomaterial(s) onto the substrate with improved resolution (e.g., fewer distortions in the applied pattern). A method utilizing a tape to deposit nanomaterial(s) onto the substrate is expected to provide increased scalability with respect to the sizes of the substrates to be patterned and also the number of surfaces to be processed per unit time.
Preferably the tape has sufficient thickness and/or rigidity to receive the composition, transfer the composition or nanomaterial, and be manipulated by the presser and tape handling components of the equipment.
In certain embodiments, a tape material comprises includes Kapton 200E, Kapton 300H, Kapton 500H, other Kapton materials, PET, TEONEX, silicone treated PET, etc. Other examples include, but are not limited to, foil (including, but not limited to, metal foil), paper, nylon, cloth, the materials listed herein as examples of mask materials, cellulose based products, fabrics, plastics, including, for example, but not limited to, ABS, acetates, butyrates, phenolics, polycarbonates, polyesters, polyethylenεs, polypropylenes, polystyrenes, polyurethanes and polyvinyl chlorides as monomers, copolymers and/or laminates. Other suitable materials and suppliers of such materials are available to those of ordinary skill in the art through various sources.
In certain embodiments, the selection of a tape material can depend upon the equipment being used in carrying out the method.
The dimensions of the tape material are preferably selected corresponding to the size of the substrate or printing area onto which nanomaterial is to be deposited.
In certain embodiments, a tape is in the form of a continuous roll, having a predetermined width and thickness.
The tape preferably has a release layer deposited on the face that will pick up the composition and deposit the composition and/or nanomaterial composition onto the substrate, depending on whether a wet or dry transfer is desired. Examples of a coating include, Parylene, Parylene-C, Parylene-N, Parylene-F, Parylene-D, Parylene-HT, Parylene AF4, other parylene compositions, other surface modifying organic molecules, and other plastics, and other surface chemistry and/or other surface treatments (e.g., energetic treatments including, but not limited to, plasma treatment, laser treatment, etc.) known or recognized in the art. In certain embodiments, the surface can be silanized.
If a coating or release layer is included on the tape, deterioration (e.g., abrasion-wear, flaking due to brittleness, etc.) of the integrity of the layer (e.g., the integrity of the attachment of the layer to the tape, smoothness of the layer, etc.) can be reduced by adjusting the shape and contour of the presser (e.g., the radius of curvature of a stamps, the radius of curvature of the rollers, the tape path itself, etc.).
In certain embodiments, the surface of the tape can be smooth (e.g., it does not include elevations and/or depressions). In other embodiments, the surface of the tape can include features (e.g., elevations and/or depressions).
As in the other embodiments discussed above, preferably a presser is not a flat surface that fully presses the tape against the substrate at a single time, to minimize trapped air between the tape and substrate when the composition or nanomaterial, as the case may be, is applied. Trapped air during the deposition step can result in an incomplete transfer.
Using a pick-up rate and deposition rate that are the same can result in ineffective transfer of the nanomaterial to the substrate in when a tape and presser comprising a roller are used. It is expected that a more effective transfer can occur when the two rates are different. See Matthew A. Meitl, et al., "Transfer Printing By Kinetic Control Of Adhesion To An Elastomeric Stamp", Nature Materials 5, 33-38 (01 Jan 2006) Letters, the disclosure of which is hereby incorporated herein by reference in its entirety.
Referring to FIG. 8 A, one or more compositions are delivered to the uppermost surface of a transfer surface from above (by, e.g., an inkcup, a micro-dispenser, an array of micro-dispensers, etc.) or from below the transfer surface (by, e.g., use of a transfer surface with a reservoir below and in connection with the uppermost surface of the transfer surface).
Referring to FIG. 8 B, a tape is passed over the uppermost surface of a transfer surface including at least one composition. A first presser (depicted as a roller with a circular cross-section) rolls over the side of the tape remote from the transfer surface to press the underside of the tape (as depicted) against the uppermost surface of the transfer surface to transfer composition from the transfer surface to the tape. Referring to FIG. 8 C, the tape is advanced to align the composition on the tape for application to the substrate upon contact when pressed by a second presser (FIG. 8 D).
If a dry transfer is desired, for example, after the predetermined pattern comprising the composition is applied to the tape, the patterned composition can be permitted to dry so that when the second presser presses the tape including the pattern against the substrate, patterned nanomaterial is transferred to the substrate. While both depicted as rollers, the first and second pressers can have the same or different shapes and/or sizes. It is envisioned that a single presser could be moved relative to the tape, transfer surface, and substrate instead of using two applicators. Optionally the surface of the applicators) used can be patterned or featureless.
Alternatively, an unpattemed layer of one or more nanomaterials can be transferred to a tape from a smooth transfer surface and deposited onto the substrate by contacting the tape to the substrate.
FlG. 9 illustrates an alternative embodiment in which one or more compositions are delivered to a surface of the tape by inkjet printing. When a composition is used which includes a carrier which dissolves or otherwise reacts with the substrate, the use of inkjet printing to deliver the composition to the surface can reduce or remove the considerations of such reaction provided the vapor pressure of the carrier and/or ambient conditions facilitate evaporation of the carrier prior to transfer of the nanomaterial to the substrate.
While FIG. 8 and 1 1 depict examples of embodiments that include a roller, a stamp or other device could alternatively be used to contact the tape to the transfer surface and/or the substrate.
Alternative techniques can be used for depositing one or more compositions onto the tape include silk screening, etc.
Methods in accordance with the invention provide advantages that can be particularly useful, for example, in depositing semiconductor nanocrystals in the fabrication of a light-emitting device (LED) including semiconductor nanocrystals.
As discussed above, in certain embodiments, the method of the invention can allow the patterned deposition of solution processable layers comprising nanomaterial (e.g., semiconductor nanocrystals, other naπoparticles, etc.) within a layered structure without disturbing the structure fidelity through the introduction of solvent to the device.
In addition, certain embodiments of the invention can be useful with existing backplane technology, and with off-the-shelf well known transport films.
The present invention is also expected to facilitate high throughput, since the nanomaterial can be introduced to the device in an singular process. Various embodiments of the invention are also expected to be compatible with processes for the manufacture of flexible displays, whether, for example, by roll-to-roll or flex-on-rigid batch mode processing.
Because semiconductor nanocrystals have narrow emission linewidths, are photoluminescent efficient, and emission wavelength tunable, they can be a desirable lumophore. The semiconductor nanocrystals optionally include organic ligands attached to the surface thereof. These zero-dimensional semiconductor structures show strong quantum confinement effects that can be harnessed in designing bottom-up chemical approaches to create complex heterostructures with electronic and optical properties that are tunable with the size and composition of the nanocrystals.
The size and composition of the semiconductor nanocrystals can be selected such that semiconductor nanocrystals emit photons at a predetermined wavelength of wavelength band in the far-visible, visible, infra-red or other desired portion of the spectrum. For example, the wavelength can be between 300 and 2,500 nm or greater, such as between 300 and 400 nm, between 400 and 700 nm, between 700 and 1100 nm, between 1100 and 2500 nm, or greater than 2500 nm.
The semiconductor nanocrystals can include semiconductor nanocrystals that emit light at the same or different wavelengths. By including an arrangement the semiconductor nanocrystals that emit light at different wavelengths, a multicolor pattern can be formed.
For example, a multicolor pattern can optionally include a repeating pattern comprising two or more different semiconductor nanocrystal materials that emit light at different wavelengths.
When two or more different color emitting compositions including nanomaterial are included as an emissive material of a display, each different color emitting nanomaterial can each independently include a plurality of semiconductor nanocrystals.
The method can include introducing onto a transfer surface a first nanomaterial including a plurality of semiconductor nanocrystals having an emission wavelength distinguishable from a second nanomaterial including a plurality of semiconductor nanocrystals.
The method can further include introducing a third or more nanomaterial s, each including a plurality of semiconductor nanocrystals, on a transfer surface. Each of the third or more nanomaterials comprises a plurality of semiconductor nanocrystals that can have an emission wavelength distinguishable from that of the other nanomaterials. The first, second, third, and other nanomaterials including pluralities of semiconductor nanocrystals can be applied to the same or different transfer surfaces, in either case, to be deposited in overlapping or non-overlapping predefined regions of the substrate. The emission wavelengths of the first, second, third, and other nanomaterials comprising pluralities of semiconductor nanocrystals can be selected from an ultraviolet, blue, green, yellow, red, cyan, magenta, infrared emission, or other wavelength, or a combination thereof.
A feature of the pattern can have a dimension of less than 10 millimeters, less than 1 millimeter, less than 100 micrometers, or less than 1 micrometer. A feature of the pattern can have a dimension of at least I centimeter, at least 10 centimeters, or at least 100 centimeters.
The surface to which the semiconductor nanocrystals are applied is typically a substrate which includes one or more device layers in-between the substrate surface and patterned semiconductor nanocrystals. Additional device layers are typically subsequently disposed over the nanocrystals. Individual saturated color LEDs can be formed at multiple locations on a single substrate to form a display.
For example, the substrate can include a layer including a hole transport material over the electrode. The method can include forming a layer including an electron transporting material over the nanomaterial. A second electrode can be applied over the layer including an electron transporting material.
An embodiment of the invention including a dry transfer process of at least the nanomaterials from the tape to the device structure is preferred when transferring semiconductor nanocrystals to an organic layer of a light-emitting device structure during device fabrication.
When depositing semiconductor nanocrystals to an inorganic layer of a light-emitting device structure, the possible reaction of the liquid of the composition with the inorganic layer can be less of a concern.
In certain embodiments including semiconductor nanocrystals, the semiconductor nanocrystals are deposited at a thickness of multiple monolayers or less, e.g., greater than three monolayers, three or less monolayers, two or less monolayers, a single monolayer, a partial monolayer, etc. The thickness of each deposited layer of semiconductor nanocrystals may vary. Preferably, the variation of the thickness at any point of the deposited nanocrystals is less than three monolayers, more preferably less than two monolayers, and most preferably less than one monolayer. In some applications, the substrate can include a backplane. The backplane includes active or passive electronics for controlling or switching power to individual pixels. Including a backplane can be useful for applications such as displays, sensors, or imagers. In particular, the backplane can be configured as an active matrix, passive matrix, fixed format, direct drive, or hybrid. The display can be configured for still images, moving images, or lighting. A lighting display can provide white light, monochrome light, or color-tunable light.
The deposition method is scalable, and can allow inexpensive manufacturing of LEDs over a large surface area.
In certain embodiments, semiconductor nanocrystals are included in a light emitting device at a monolayer thickness. A monolayer can provide the beneficial light emission properties of semiconductor nanocrystals while minimizing the impact on electrical performance.
A light emitting device can include two layers separating two electrodes of the device. The material of one layer can be chosen based on the material's ability to transport holes, or the hole transporting layer (HTL). The material of the other layer can be chosen based on the material's ability to transport electrons, or the electron transporting layer (ETL). The electron transporting layer typically includes an electroluminescent layer. When a voltage is applied, one electrode injects holes (positive charge carriers) into the hole transporting layer, while the other electrode injects electrons into the electron transporting layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an exciton is formed, which can recombine to emit light.
When the electron and hole localize on a nanocrystal, emission can occur at an emission wavelength. The emission has a frequency that corresponds to the band gap of the quantum confined semiconductor material. The band gap is a function of the size of the nanocrystal. Nanocrystals having small diameters can have properties intermediate between molecular and bulk forms of matter. For example, nanocrystals based on semiconductor materials having small diameters can exhibit quantum confinement of both the electron and hole in all three dimensions, which leads to an increase in the effective band gap of the material with decreasing crystallite size. Consequently, both the optical absorption and emission of nanocrystals shift to the blue, or to higher energies, as the size of the crystallites decreases. The emission from the nanocrystal can be a narrow Gaussian emission band that can be tuned through the complete wavelength range of the ultraviolet, visible, or infrared regions of the spectrum by varying the size of the nanocrystal, the composition of the nanocrystal, or both. For example, CdSe can be tuned in the visible region and InAs can be tuned in the infrared region. The narrow size distribution of a population of nanocrystals can result in emission of light in a narrow spectral range. The population can be monodisperse and can exhibit less than a 15% rms deviation in diameter of the nanocrystals, preferably less than 10%, more preferably less than 5%. Spectral emissions in a narrow range of no greater than about 75 nm, preferably 60 nm, more preferably 40 nm, and most preferably 30 nm full width at half max (FWHM) can be observed. The breadth of the emission decreases as the dispersity of nanocrystal diameters decreases. Semiconductor nanocrystals can have high emission quantum efficiencies such as greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%.
A light emitting device can have a structure such as shown in FlG. 10, in which a first electrode 1302, a first layer 1303 in contact with the electrode 1302, a second layer 1304 in contact with the layer 1303, and a second electrode 1305 in contact with the second layer 1304. First layer 1303 can be a hole transporting layer and second layer 1304 can be an electron transporting layer. At least one layer can be non-polymeric. Alternatively, a separate emissive layer (not shown in FIG. 10) can be included between the hole transporting layer and the electron transporting layer. One of the electrodes of the structure is in contact with a substrate 1301. Each electrode can contact a power supply to provide a voltage across the structure. Electroluminescence can be produced by the emissive layer of the heterostructure when a voltage of proper polarity is applied across the heterostructure. First layer 1303 can include a plurality of semiconductor nanocrystals, for example, a substantially monodisperse population of nanocrystals. Alternatively, a separate emissive layer can include the plurality of nanocrystals. In certain embodiments, a layer that includes semiconductor nanocrystals is preferably a monolayer of nanocrystalSi
The substrate can be opaque or transparent. The substrate can be rigid or flexible. The substrate can be plastic, metal or glass. The first electrode can be, for example, a high work function hole-injecting conductor, such as an indium tin oxide (ITO) layer. Other first electrode materials can include gallium indium tin oxide, zinc indium tin oxide, titanium nitride, or polyaniline. The second electrode can be, for example, a low work function (e.g., less than 4.0 eV), electron- injecting, metal, such as Al, Ba, Yb, Ca, a lithium-aluminum alloy (Li:Al), or a magnesium-silver alloy (Mg:Ag). The second electrode, such as Mg:Ag, can be covered with an opaque protective metal layer, for example, a layer of Ag for protecting the cathode layer from atmospheric oxidation, or a relatively thin layer of substantially transparent ITO. The first electrode can have a thickness of about 500 Angstroms to 4000 Angstroms. The first layer can have a thickness of about 50 Angstroms to about 1000 Angstroms. The second layer can have a thickness of about 50 Angstroms to about 1000 Angstroms. The second electrode can have a thickness of about 50 Angstroms to greater than about 1000 Angstroms.
The electron transporting layer (ETL) can be a molecular matrix. The molecular matrix can be non-polymeric. The molecular matrix can include a small molecule, for example, a metal complex. For example, the metal complex can be a metal complex of 8-hydroxyquinoline. The metal complex of 8-hydroxyquinoline can be an aluminum, gallium, indium, zinc or magnesium complex, for example, aluminum tris(8-hydroxyquinoline) (AIq3). Other classes of materials in the ETL can include metal thioxinoid compounds, oxadiazole metal chelates, triazoles, sexithiophene derivatives, pyrazine, and styrylanthracene derivatives. The hole transporting layer can include an organic chromophore. The organic chromophore can be a phenyl amine, such as, for example, N,N'- diphenyl-N,N'-bis(3-methylphenylKl,l'-biphenyl)-4,4'-diamine (TPD), 4-4'-N,N'-dicarbazolyl- biphenyl (CBP), 4,4-. bis[N-(l-naphthyl)-N-phenylamino]biphenyl (NPD), etc. The HTL can include a polyaniline, a polypyrrole, a poly(phenylene vinylene), copper phthalocyanine, an aromatic tertiary amine or polynuclear aromatic tertiary amine, a 4,4'-bis(9-carbazolyl)-l,l'-biphenyl compound, or an N,N,N',N'-tetraarylbenzidine.
The layers can be deposited on a surface of one of the electrodes by spin coating, dip coating, vapor deposition, or other thin film deposition methods. See, for example, M. C. Schlamp, et al, J. Appl. Phys., 82, 5837-5842, (1997); V. Santhanam, et al., Langmuir, 19, 7881-7887, (2003); and X. Lin, et al., J. Phys. Chem. B, 105, 3353-3357, (2001), each of which is incorporated by reference in its entirety. The second electrode can be sandwiched, sputtered, or evaporated onto the exposed surface of the solid layer. One or both of the electrodes can be patterned. The electrodes of the device can be connected to a voltage source by electrically conductive pathways. Upon application of the voltage, light is generated from the device.
Preferably, semiconductor nanocrystals are processed in a controlled (oxygen-free and moisture-free) environment, preventing the quenching of luminescent efficiency during the fabrication process.
Other multilayer structures may be used to improve the device performance (see, for example, U.S. Patent Application Nos. 10/400,907 and 10/400,908, filed March 28, 2003, each of which is incorporated by reference in its entirety). A blocking layer, such as an electron blocking layer (EBL), a hole blocking layer (HBL) or a hole and electron blocking layer (eBL), can be introduced in the structure. A blocking layer can include 3-(4-biphenylyl)-4-phenyl-5-tert- butylphenyl-l,2,4-triazole (TAZ), 3,4,5-triphenyl-l,2,4-triazole, 3,5-bis(4-tert-butylphenyl)-4- phenyl-l,2,4-triazole, bathocuproine (BCP), 4,4',4"-tris{N-(3-methylphenyl)-N- phenylamino}triphenylamine (m-MTDATA), polyethylene dioxythiophene (PEDOT), 1 ,3-bis(5-(4- diphenylamino)phenyl-l,3,4-oxadiazol-2-yl)benzene, 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-l,3,4- oxadiazole, 1 ,3 -bis[5-(4-( 1 , 1 -dimethy lethyl)phenyl)- 1 ,3 ,4-oxad iazol-2-y l]benzene, 1 ,4-bis(5-(4- diphenyl-amino)phenyl-l,3,4-oxadiazol-2-yl)benzene, or l,3,5-tris[5-(4-(l,l-dimethylethyl)- pheny I)- 1,3 ,4-oxad iazol-2-y 1] benzene. A hole-injection layer (HDL) (e.g., Poly(3,4- ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT PSS)) can optionally be introduced between the first electrode and HTL.
A detailed example of one embodiment of a device structure (from bottom to top) can include a 150 nm indium tin oxide (ITO) anode layer, a 70 nm Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT.PSS) hole injection layer (HIL), a 50 nm N,N'-Bis(3- methylphenyl)-N,N'-bis-(phenyl)-spiro (spiro-TPD) hole transport layer, a 5-10 nm semiconductor nanocrystal emissive layer, a 50 nm 2,2',2"-(l,3,5-benzinetriyl)- tris(l -phenyl- 1 -H-benzimidazole) (TPBi) hole-blocking/electron transporting layer and a 0.5 nm LiF/100 nm Al cathode layer. The ITO layer can be deposited, patterned and cleaned using industry standard techniques. The PEDOTrPSS layer can be deposited by spin coating followed by bake out at 125 C for 20 minutes. AU other organic and metal layers can be thermally evaporated in a high vacuum chamber. Prior to testing and operation the entire device is preferably encapsulated using, for example, a sealant in a dry nitrogen environment (<1 ppm O2, <1 ppm H2O). A sealant of the type used in OLEDs is one example of a sealant that can be used.
Examples of semiconductor nanocrystals useful in the above described device include, for example, and without limitation, those described in U.S. Patent Application Nos. 60/825373, filed 12 September 2006 and 60/825374m filed 12 September 2006.
The performance of light emitting devices can be improved by increasing their efficiency, narrowing or broadening their emission spectra, or polarizing their emission. See, for example, Bulovic et al., Semiconductors and Semimetals 64, 255 (2000), Adachi et al., Appl. Phys. Lett. 78, 1622 (2001), Yamasaki et al., Appl. Phys. Lett. 76, 1243 (2000), Dirr et al., Jpn. J. Appl. Phys. 37, 1457 (1998), and D'Andrade et al., MRS Fall Meeting, BB6.2 (2001 ), each of which is incorporated herein by reference in its entirety. Nanocrystals can be included in efficient hybrid organic/inorganic light emitting devices. The narrow FWHM of nanocrystals can result in saturated color emission. This can lead to efficient nanocrystal-light emitting devices even in the red and blue parts of the visible spectrum, since in nanocrystal emitting devices no photons are lost to infrared and UV emission. The broadly tunable, saturated color emission over the entire visible spectrum of a single material system is unmatched by any class of organic chromophores (see, for example, Dabbousi et al, J. Phys. Chem. 101 , 9463 (1997), which is incorporated by reference in its entirety). A monodisperse population of nanocrystals will emit light spanning a narrow range of wavelengths. A device including more than one size of nanocrystal can emit light in more than one narrow range of wavelengths. The color of emitted light perceived by a viewer can be controlled by selecting appropriate combinations of nanocrystal sizes and materials in the device. The degeneracy of the band edge energy levels of nanocrystals facilitates capture and radiative recombination of all possible excitons, whether generated by direct charge injection or energy transfer. The maximum theoretical nanocrystal-light emitting device efficiencies are therefore comparable to the unity efficiency of phosphorescent organic light emitting devices. The excited state lifetime (τ) of the nanocrystal is much shorter (τ ~10 ns) than a typical phosphor (τ > 0.5 μs), enabling nanocrystal-light emitting devices to operate efficiently even at high current density.
Devices can be prepared that emit visible or infrared light. The size and material of a semiconductor nanocrystal can be selected such that the nanocrystal emits visible or infrared light of a selected wavelength. The wavelength can be between 300 and 2,500 nm or greater, for instance between 300 and 400 nm, between 400 and 700 nm, between 700 and 1 100 nm, between 1 100 and 2500 nm, or greater than 2500 nm.
Individual devices can be formed at multiple locations on a single substrate to form a display. The display can include devices that emit at different wavelengths. By patterning the substrate with arrays of different color-emitting semiconductor nanocrystals, a display including pixels of different colors can be formed.
Besides being useful to deposit nanomaterials in fabricating of display devices, methods in accordance with the invention can be used to deposit various other materials, especially other materials comprising nanoparticles, in fabricating a variety of lighting, electronic, or optoelectronic devices.
For example, an unpatterned layer comprising nanomaterial comprising a white light- emitting mixture of semiconductor nanocrystals can be deposited onto a substrate by a method in accordance with the invention. The mixture includes semiconductor nanocrystals with different sizes and compositions which can simultaneously emit light at different wavelengths to achieve white light emission. The mixture of semiconductor nanocrystals are deposited as a layer in a device structure that also includes a hole transport layer and/or an electron transport layer. The device may used to provide general lighting or may be included in a display, e.g., a liquid crystal display, to provide backlighting. Alternatively, the device may further include a color filter to provide a full-color display. See U.S. Patent Application No. 20060043361 entitled "White Light- Emitting Organic-Inorganic Hybrid Electroluminescence Device Comprising Semiconductor Nanocrystals", of Lee et al, published 2 March 2006, the disclosure of which is hereby incorporated herein by reference in its entirety.
Another example includes depositing nanomaterial comprising a plurality of semiconductor nanocrystals by a method in accordance with the invention in fabrication of a photodetector device or array of photodetector devices. A photodetector device includes one or more nanomaterials comprising a plurality of semiconductor nanocrystals which are selected based upon absorption properties. When included in a photodetector, semiconductor nanocrystals are engineered to produce a predetermined electrical response upon absorption of a particular wavelength, typically in the IR or MIR region of the spectrum. Examples of photodetector devices including semiconductor nanocrystals are described in "A Quantum Dot Heterojunction Photodetector" by Alexi Cosmos Arango, Submitted to the Department of Electrical Engineering and Computer Science, in partial fulfillment of the requirements for the degree of Masters of Science in Computer Science and Engineering at the Massachusetts Institute of Technology, February 2005, the disclosure of which is hereby incorporated herein by reference in its entirety.
In one embodiment, a method of fabricating photodetector device includes applying a layer including nanomaterial to a surface of a tape from a transfer surface and depositing nanomaterial onto a substrate. In one embodiment, the nanomaterial including a plurality of semiconductor nanocrystals can be deposited on the substrate as an unpatterned layer.
In another embodiment, a method of fabricating an array of photodetector devices includes applying a layer comprising nanomaterial to surface of a tape from a transfer surface and depositing nanomaterial onto a substrate. In one embodiment, the nanomaterial including a plurality of semiconductor nanocrystals can be deposited on the substrate as a patterned layer. The substrate can further include an electrode. A second electrode can be deposited over the nanomaterial. Optionally, an electron transport layer can be included between the nanomaterial and the cathode electrode and/or a hole transport layer can be included between the anode electrode and the nanomaterial.
A method of fabricating a photodetector device or array of devices can optionally include depositing one or more nanomaterials in a predetermined arrangement (patterned or unpatterned). As discussed above, nanomaterial can optionally be included in a composition.
Methods in accordance with the invention can also be used in deposition nanomaterials in the fabrication of memory devices. An example of a nonvolatile device is described in U.S. Patent Application No. 10/958,659, entitled "Non- Volatile Memory Device", of Bawendi et al., filed 6 October 2004, the disclosure of which is hereby incorporated herein by reference in its entirety. As discussed above, nanomaterial can optionally be included in a composition.
Other techniques, methods and applications that may be useful with the present invention are described in, U.S. Provisional Patent Application 60/792,084, of Maria J. Anc, for "Methods Of Depositing Material, Methods Of Making A Device, And System", filed 14 April 2006; U.S. Provisional Patent Application 60/792,086, of Marshall Cox, et al, for "Methods Of Depositing Nanomaterial & Methods Of Making A Device", filed on 14 April 2006, U.S. Provisional Patent Application 60/792,167 of Seth Coe-Sullivan, et al, for "Articles For Depositing Materials, Transfer Surfaces, And Methods", filed on 14 April 2006; U.S. Provisional Patent Application No. 60/792,083 of LeeAnn Kim et al., for "Applicator For Depositing Materials And Methods", filed 14 April 2006; and U.S. Provisional Patent Application No. 60/793,990 of LeeAnn Kim et al., for "Applicator For Depositing Materials And Methods", filed 21 April 2006; the disclosures of each of which is hereby incorporated herein by reference in its entirety.
As used herein, "top" and "bottom" are relative positional terms, based upon a location from a reference point. For example, "top" of a device structure means farthest away from the substrate, while "bottom" means closest to the substrate. For example, for a light-emitting device that optionally includes two electrodes, the bottom electrode is the electrode closest to the substrate, and is generally the first electrode fabricated; the top electrode is the electrode that is more remote from the substrate, on the top side of the light-emitting material. The bottom electrode has two surfaces, a bottom surface closest to the substrate, and a top surface further away from the substrate. Where, e.g., a first layer is described as disposed or deposited "over" a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is otherwise specified. For example, a cathode may be described as "disposed over" an anode, even though there are various organic and/or inorganic layers in between. As used herein, the singular forms "a", "an" and "the" include plural unless the context clearly dictates otherwise. Thus, for example, reference to an emissive material includes reference to one or more of such materials.
When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.
In various instances herein, a semiconductor nanocrystal is referred to by the term "nanocrystal".
It will be apparent to those skilled in the art that various modifications can be made in the methods, articles and systems of the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
All the patents and publications mentioned above and throughout are incorporated in their entirety by reference herein.
Other embodiments of the present invention will be apparent to those skilled in the art from consideration of the present specification and practice of the present invention disclosed herein. It is intended that the present specification and examples be considered as exemplary only with a true scope and spirit of the invention being indicated by the following claims and equivalents thereof.

Claims

WHAT IS CLAIMED IS:
1. A method for depositing nanomaterial onto a substrate comprising: applying a composition comprising nanomaterial to a surface of a tape, and contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate.
2. A method in accordance with claim 1 wherein the composition is selectively applied to the tape surface.
3. A method in accordance with claim 2 wherein the nanomaterial is applied to the tape from a transfer surface.
4. A method in accordance with claim 2 wherein nanomaterial is deposited onto the substrate in a predetermined pattern.
5. A method in accordance with claim 2 wherein the composition is applied to the tape surface by inkjet printing.
6. A method in accordance with claim 1 wherein the nanomaterial is deposited onto the substrate as an unpatterned layer.
7. A method in accordance with claim 1 wherein the method is repeated one or more times to deposit one or more nanomaterials onto the substrate.
8. A method in accordance with claim 1 wherein each of the nanomaterials is deposited onto the substrate in a predetermined pattern.
9. A method in accordance with claim 1 wherein the nanomaterial comprises semiconductor nanocrystals.
10. A method in accordance with claim 1 wherein the composition further includes a carrier medium.
1 1. A method in accordance with claim 1 1 wherein the carrier medium comprises liquid.
12. A method in accordance with claim 2 wherein the transfer surface includes one or more grooves.
13. A method in accordance with claim 2 wherein the transfer surface is smooth.
14. A method in accordance with claim 2 wherein the transfer surface is surface treated.
15. A method in accordance with claim 12 wherein the transfer surface is surface treated.
16. A method in accordance with claim 1 1 wherein the surface treatment within the one or more grooves is different from the surface treatment outside of the one or more grooves.
17. A method in accordance with claim 1 1 wherein the composition is substantially free of liquid when applied to the tape surface.
18. A method in accordance with claim 4 wherein the composition is substantially free of liquid when deposited to the substrate.
19. A method in accordance with claim 5 wherein a layer including the composition is applied to the tape.
20. A method in accordance with claim 19 wherein the layer is unpatterned.
21. A method in accordance with claim 1 wherein the composition is applied to the tape in a patterned arrangement.
22. A method in accordance with claim 21 wherein the patterned arrangement comprises a feature having a dimension of less than 1000 micrometers.
23. A method in accordance with claim 21 wherein the patterned arrangement comprises a feature having a dimension of less than 100 micrometers.
24. A method in accordance . with claim 21 wherein the patterned arrangement comprises a feature having a dimension of less than 10 micrometers.
25. A method in accordance with claim 1 wherein the tape surface is substantially free of elevations and depressions.
26. A method in accordance with claim 1 wherein the tape comprises a surface including elevations and/or depressions in a predetermined pattern.
27. A method in accordance with claim 1 further comprising modifying the surface of the tape before applying a composition to the surface.
28. A method in accordance with claim 27 wherein modifying the surface of the tape includes contacting the surface of the tape with a surface treatment composition selected to release at least a portion of the nanomaterial from the tape upon contact with a substrate.
29. A method in accordance with claim 28 wherein the surface treatment composition includes an aromatic organic polymer.
30. A method in accordance with claim 1 wherein the tape is included in a roll to roll configuration.
31. A method in accordance with claim 1 wherein the nanomaterial comprises semiconductor nanocrystals.
32. A method in accordance with claim 1 wherein the nanomaterial comprises two or more different nanomaterials, wherein each nanomaterial comprises a plurality of semiconductor nanocrystals.
33. A method in accordance with claim 31 wherein the semiconductor nanocrystals comprise a core/shell structure.
34. A method in accordance with claim 33 wherein the core comprises a Group IV element, a Group H-VI compound, a Group H-V compound, a Group HI-VI compound, a Group HI-V compound, a Group FV-VI compound, a Group I-III-VI compound, a Group H-IV-VI compound, a Group H-IV-V compound, alloys thereof, and/or mixtures thereof.
35. A method in accordance with claim 34 wherein the shell comprises a Group FV element, a Group H-VI compound, a Group H-V compound, a Group III-VI compound, a Group HI-V compound, a Group IV-VI compound, a Group I-III-VI compound, a Group II-IV-VI compound, a Group II-IV-V compound, alloys thereof, and/or mixtures thereof.
36. A method in accordance with claim 32 wherein the semiconductor nanocrystals include at least one ligand attached to the surface.
37. A method in accordance with claim 1 wherein two or more compositions are applied to the tape.
38. A method in accordance with claim 37 wherein the two or more compositions are applied to the tape in a predetermined arrangement.
39. A method in accordance with claim 3 wherein the two or more compositions are applied to the tape in a predetermined arrangement from the transfer surface.
40. A method in accordance with claim 37 wherein each of the two or more compositions comprises a nanomaterial comprising a plurality of semiconductor nanocrystals, and wherein the two or more different compositions are disposed on the transfer surface in a predetermined pattern.
41. A method in accordance with claim 40 wherein the predetermined pattern comprising two or more different nanomaterials is deposited onto the substrate.
42. A method in accordance with claim 1 wherein the tape comprises PET.
43. A method in accordance with claim 1 wherein the tape comprises Kapton.
44. A method in accordance with claim I wherein the tape comprises plastic.
45. A method in accordance with claim 1 wherein the tape comprises foil.
46. A method in accordance with claim 1 wherein the tape comprises paper.
47. A method in accordance with claim 1 wherein the tape comprises nylon.
48. A method in accordance with claim 1 wherein the tape comprises cloth.
49. A method of making a light emitting device, comprising: applying a composition comprising semiconductor nanocrystals to a surface of a tape, and contacting the surface of the tape including the semiconductor nanocrystals to the substrate under conditions to cause at least a portion of the semiconductor nanocrystals to deposit onto the substrate.
50. A method in accordance with claim 49 wherein the substrate includes an electrode, a hole transport material, an electron transport material, a hole injection material, an electron injection material, or a combination thereof.
51. A method of forming a device comprising: applying a composition comprising nanomaterial to a surface of a tape; contacting the surface of the tape including the nanomaterial to a substrate a substrate including a first electrode under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate; and arranging a second electrode opposed to the first electrode.
52. A method in accordance with claim 51 wherein a predetermined pattern comprising nanomaterial is transferred onto the substrate from the surface of the tape.
53. A method in accordance with claim 51 wherein the nanomaterial includes a plurality of semiconductor nanocrystals.
54. A method in accordance with claim 53 wherein the plurality of semiconductor nanocrystals forms a layer on the substrate.
55. A method in accordance with 54 wherein the layer is a multilayer of semiconductor nanocrystals.
56. A method in accordance with claim 54 wherein the layer is a monolayer of semiconductor nanocrystals.
57. A method in accordance with claim 54 wherein the layer is a partial monolayer of semiconductor nanocrystals.
58. A method in accordance with claim 50 wherein the nanomaterial forms a layer on the substrate.
59. A method in accordance with claim 57 wherein the layer is a monolayer of the nanomaterial.
60. A method in accordance with claim 57 wherein the layer is a partial monolayer of the nanomaterial.
61. A method in accordance with claim 51 wherein the nanomaterial forms a pattern on the substrate.
62. A method in accordance with claim 51 further comprising modifying the surface of the tape before applying the nanomaterial.
63. A method in accordance with claim 62 wherein modifying the surface of the tape includes contacting the surface of the tape with a composition selected to release at least a portion of the nanomaterial from the tape upon contact with a substrate.
64. A method in accordance with claim 63 wherein the composition includes an aromatic organic polymer.
65. A method in accordance with claim 51 further comprising introducing two or more compositions comprising nanomaterial onto the transfer surface.
66. A method in accordance with claim 65 wherein each of the nanomaterial s independently include a plurality of semiconductor nanocrystals.
67. A method in accordance with claim 66 wherein each of the plurality of semiconductor nanocrystals has an emission wavelength distinguishable from the other semiconductor nanocrystals.
68. A method in accordance with claim 67 wherein the emission wavelengths of the pluralities of semiconductor nanocrystals are selected from an ultraviolet, blue, green, yellow, red, or infrared emission wavelength, or a combination thereof.
69. A method in accordance with claim 61 wherein a feature of the pattern has a dimension of less than 10 millimeters.
70. A method in accordance with claim 61, wherein a feature of the pattern has a dimension of less than 1 millimeter.
71 . A method in accordance with claim 61 wherein a feature of the pattern has a dimension of less than 100 micrometers.
72. A method in accordance with claim 61 wherein a feature of the pattern has a dimension of less than 1 micrometer.
73. A method in accordance with claim 61 wherein a feature of the pattern has a dimension of at least 1 centimeter.
74. A method in accordance with claim 61 wherein a feature of the pattern has a dimension of at least 10 centimeters.
75. A method in accordance with claim 61 wherein a feature of the pattern has a dimension of at least 100 centimeters.
76. A method in accordance with claim Sl wherein the substrate includes a layer including a hole transport material over the first electrode.
77. A method in accordance with claim 76 further comprising forming a layer including an electron transporting material over the nanomaterial.
78. A method in accordance with claim 77 wherein the second electrode is applied over the layer including the electron transporting material.
79. A method in accordance with claim S 1 further comprising applying each of two or more compositions comprising nanomaterial to individual transfer surfaces, wherein each composition is applied to the tape from a separate transfer surface; and contacting the surface of tape to the substrate, thereby transferring at least a portion of the one or more additional compositions comprising plurality of semiconductor nanocrystals onto the substrate.
80. A method in accordance with claim 79 wherein each of the nanomaterials independently includes a plurality of semiconductor nanocrystals.
81. A method in accordance with claim 80 wherein each of the nanomaterials has an emission wavelength distinguishable from each of the other nanomaterials.
82. A method in accordance with claim 81 wherein the emission wavelength of each nanomaterial is selected from an ultraviolet, blue, green, yellow, red, cyan, magenta, infrared emission wavelength, or a combination thereof.
83. A method in accordance with claim Sl wherein the device comprises a photodetector.
84. A method in accordance with claim Sl wherein the device comprises an array of photodetectors.
85. A method in accordance with claim Sl wherein the device comprises a nonvolatile random memory device.
86. A method for depositing nanomaterial onto a substrate comprising: applying a composition comprising nanomaterial to a surface of a tape from a transfer surface, contacting the surface of the tape including the nanomaterial to the substrate under conditions to cause at least a portion of the nanomaterial to deposit onto the substrate.
87. A method in accordance with claim 86 wherein the nanomaterial comprises a semiconductor nanocrystal.
88. A method in accordance with claim 1 wherein the nanomaterial comprises a nanotube (such as a single walled or multi-walled carbon nanotube), a nanowire, a nanorod, a dendrimer, organic nanocrystal, organic small molecule, other nano-scale or micro-scale material or mixtures thereof.
89. A method in accordance with claim 86 wherein the nanomaterial comprises a nanotube (such as a single walled or multi-walled carbon nanotube), a nanowire, a nanorod, a dendrimer, organic nanocrystal, organic small molecule, other nano-scale or micro-scale material or mixtures thereof.
90. A method in accordance with claim 28 wherein the surface treatment composition includes an molecular organic compound.
91. A method in accordance with claim 63 wherein the composition includes an molecular organic compound.
92. A method in accordance with claim 51 further comprising applying each of two or more compositions comprising nanomaterial to individual transfer surfaces, wherein each composition is applied to a separate section of tape from a separate transfer surface; and contacting the surface of each section of tape to the substrate, thereby transferring at least a portion of the one or more additional compositions comprising plurality of semiconductor nanocrystals onto the substrate.
93. A method in accordance with any of claim 1, 49, and S l wherein a mask including a predetermined arrangement of one or more apertures is positioned on the substrate prior to contacting the surface of the tape to the substrate through at least one aperture of the mask.
94. The new, useful and unobvious processes, machines, manufactures, and compositions of matter, as shown and described herein.
95. New, useful and unobvious improvements of processes, machines, manufactures, and compositions of matter, as shown and described herein.
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