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WO2021172408A1 - Dispositif à semi-conducteur et son procédé de fabrication - Google Patents

Dispositif à semi-conducteur et son procédé de fabrication Download PDF

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Publication number
WO2021172408A1
WO2021172408A1 PCT/JP2021/007036 JP2021007036W WO2021172408A1 WO 2021172408 A1 WO2021172408 A1 WO 2021172408A1 JP 2021007036 W JP2021007036 W JP 2021007036W WO 2021172408 A1 WO2021172408 A1 WO 2021172408A1
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Prior art keywords
conductive film
film
semiconductor device
region
organic semiconductor
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PCT/JP2021/007036
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English (en)
Japanese (ja)
Inventor
達生 長谷川
暁 北原
井上　悟
俊人 荒井
光弘 井川
Original Assignee
国立大学法人 東京大学
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Priority to JP2022503677A priority Critical patent/JPWO2021172408A1/ja
Publication of WO2021172408A1 publication Critical patent/WO2021172408A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
    • H01L29/66409—Unipolar field-effect transistors
    • H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass

Definitions

  • One aspect of the present invention relates to a semiconductor device including a thin film transistor. Further, one aspect of the present invention relates to a method for manufacturing the semiconductor device using a coating process.
  • An organic semiconductor film can be formed by dissolving an organic semiconductor compound in a solvent and applying the obtained solution. While a vacuum process is required to form an inorganic semiconductor film made of silicon or the like, an organic semiconductor film can be formed without using such a vacuum process. Therefore, its manufacturing cost is relatively low. Further, since it is not necessary to reduce the pressure in the chamber where the film is formed to vacuum, it is relatively easy to form the organic semiconductor film in the large chamber. In this case, it is possible to manufacture a semiconductor element including an organic semiconductor film in a large area and in a large amount. In addition, the organic semiconductor film is formed without using the high temperature heating process required for forming the inorganic semiconductor film.
  • the substrate on which the organic semiconductor film is formed is not limited to the heat-resistant substrate, and may be a flexible substrate made of a relatively inexpensive plastic material.
  • the substrate on which the organic semiconductor film is formed is not limited to the heat-resistant substrate, and may be a flexible substrate made of a relatively inexpensive plastic material.
  • An example of a semiconductor device containing an organic semiconductor film is a thin film transistor in which a channel is formed in the organic semiconductor film.
  • a semiconductor device containing an organic semiconductor film is a thin film transistor in which a channel is formed in the organic semiconductor film.
  • its manufacturing process for example, a technique of selectively applying an organic semiconductor layer only to a part that functions as a channel
  • characteristics for example, high carrier mobility, from on to off. It is important to establish that hysteresis does not occur (hysteresis-free) and the drain current changes abruptly in the vicinity of the threshold voltage) during switching of the above or vice versa.
  • the gate electrode film and the semiconductor film are arranged so as to overlap with each other via the gate insulating film.
  • a structure in which a semiconductor film is arranged on a gate electrode film via a gate insulating film (bottom gate type structure) is often adopted. Then, depending on the voltage applied to the gate electrode film, it is determined whether or not the carrier channel is formed in the region near the gate insulating film of the semiconductor film.
  • the carrier conduction in the organic semiconductor film included in the thin film transistor is strongly influenced by the physical and chemical properties of the gate insulating film at the interface with the organic semiconductor film.
  • Patent Document 1 discloses that when SiO 2 is used as the gate insulating film, the hydroxyl groups, oxygen and water existing on the surface thereof serve as trap sites for carrier conduction.
  • Non-Patent Document 1 discloses that a treatment (SAM treatment) for forming a self-assembled monolayer at the interface of the gate insulating film is effective.
  • SAM treatment a treatment for forming a self-assembled monolayer at the interface of the gate insulating film is effective.
  • an organic thin film transistor using a highly water-repellent fluororesin (Cytop (registered trademark)) as a gate insulating film and a rubrene single crystal as an organic semiconductor film is hysteresis-free and remarkably.
  • Patent Document 1 and Non-Patent Document 3 disclose that the entire surface of the gate insulating film is subjected to SAM treatment, and then the portion other than the portion that becomes the channel forming region is liquefied by exposure treatment. As a result, it is possible to prevent the solution containing the material constituting the applied organic semiconductor film as a solute from being repelled at the portion where the exposure treatment is performed. Further, the organic semiconductor film can be left without being repelled even in a portion surrounded by the exposed portion.
  • Non-Patent Document 4 discloses that the entire surface of the gate insulating film is subjected to SAM treatment, and then only a portion that becomes a channel forming region is liquefied by exposure treatment. Thereby, it is possible to apply the solution containing the material constituting the organic semiconductor film as a solute only to the portion where the exposure treatment has been performed. Further, in Patent Document 2, a method of forming a repellent pattern utilizing a change in the density of a self-assembled monolayer and applying a solution containing a material constituting an organic semiconductor film as a solute is applied only to the parent liquid portion. It is shown.
  • Non-Patent Document 5 discloses that a fluororesin is used as the process bank.
  • One aspect of the present invention is to provide a semiconductor device including a thin film transistor that can be manufactured more easily than a conventional method.
  • the organic semiconductor film Prior to the formation of the organic semiconductor film on the insulating film having liquid repellency against the solvent which is the main component of the solution containing the material constituting the organic semiconductor film as a solute, the present inventors have a parent for the solvent. It has been found that the organic semiconductor film can be formed at a desired position, for example, in a channel forming region of a transistor by forming a film having a liquid conductive film in a desired shape.
  • the conductive film that functions as a source and drain in the layer above the insulating film that functions as the gate insulating film and under the organic semiconductor film has a desired shape. It is a gist that a conductive film having a desired shape is provided separately from the conductive film that functions as a source and a drain. Further, in the method for manufacturing a semiconductor device according to one aspect of the present invention, a conductive film that functions as a source and a drain is desired in a layer above the insulating film that functions as a gate insulating film and under the organic semiconductor film. The gist is to form a film into a shape, or to form a conductive film having a desired shape separately from the conductive film that functions as a source and a drain.
  • the second conductive film includes a portion extending along the first direction
  • the third conductive film includes a first portion located in the first direction and a second conductive film as viewed from the second conductive film. The second portion located in the second direction orthogonal to the first direction and the third portion located in the third direction opposite to the second direction when viewed from the region between the conductive film and the first portion, and the third portion.
  • the first part, 2 At least a part of the portion and at least a part of the third portion extend continuously, and the surface free energy of the insulating film is smaller than the surface free energy of the second conductive film and the surface free energy of the third conductive film.
  • the semiconductor device is one aspect of the present invention.
  • a step of forming a first conductive film, a step of forming an insulating film on the first conductive film, and a step of irradiating the first region and the second region of the insulating film with ultraviolet rays includes a step of forming a second conductive film and a third conductive film in each of the first region and the second conductive film, and a step of forming an organic semiconductor film on the insulating film, the second conductive film and the third conductive film, respectively.
  • the first region extends along the first direction, and the second region is from the first portion located in the first direction when viewed from the first region and the region between the first region and the first portion.
  • the second part located in the second direction orthogonal to the first direction, the third part located in the third direction opposite to the second direction, and the opposite of the first direction when viewed from the second part.
  • At least a part of the contact angle of the solvent which is the main component of the solution containing the material constituting the organic semiconductor film as a solute, with respect to the gate insulating film is determined by the second conductive film and the third conductive film of the solvent.
  • a method for manufacturing a semiconductor device which includes a step of forming an organic semiconductor film having a contact angle larger than the contact angle with respect to each of the films and a step of applying a solution along a fourth direction, is also an aspect of the present invention.
  • a thin film transistor having an organic semiconductor film without going through complicated steps such as a method using a conventional repellent pattern and a method using a bank.
  • FIG. 2 is a cross-sectional view taken along the line AA'shown in FIG. 1A. Top view showing a state in which the organic semiconductor film 7 is removed from the semiconductor device shown in FIG. 1A.
  • FIG. 3A is a cross-sectional view taken along the line BB'shown in FIG. 3A. Top view showing a state in which the organic semiconductor film 25 is removed from the semiconductor device shown in FIG. 3A.
  • the cross-sectional view which shows an example of the manufacturing method of the semiconductor device of one aspect of this invention.
  • the cross-sectional view which shows an example of the manufacturing method of the semiconductor device of one aspect of this invention.
  • FIG. 5 is a side view showing an example of a method of applying a solution containing a material constituting the gate electrode film 15 as a solute.
  • the top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute.
  • FIG. 6 is a cross-sectional view taken along the line CC'shown in FIG. 7A.
  • the top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute.
  • FIG. 5 is a side view showing an example of a method of applying a solution containing a material constituting the gate electrode film 15 as a solute.
  • the top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute.
  • FIG. 6 is a cross-sectional view taken along the line CC'shown in FIG. 7A.
  • the top view which shows an example of the coating method of the solution containing the material constitu
  • FIG. 6 is a cross-sectional view taken along the line CC'shown in FIG. 8A.
  • the top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute.
  • FIG. 9 is a cross-sectional view taken along the line CC'shown in FIG. 9A.
  • the top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute.
  • FIG. 4 is a cross-sectional view taken along the line CC'shown in FIG. 10A.
  • the top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute.
  • FIG. 4 is a cross-sectional view taken along the line CC'shown in FIG.
  • FIG. 10A The cross-sectional view which shows the modification example of the semiconductor device.
  • FIGS. 1A and 1B are diagrams showing an example of a semiconductor device according to an aspect of the present invention. Specifically, FIG. 1A is a top view of the semiconductor device, and FIG. 1B is a cross-sectional view taken along the line segment AA'of FIG. 1A. Further, FIG. 2 is a top view showing a state in which the organic semiconductor film 7 is removed from the semiconductor device shown in FIG. 1A.
  • the semiconductor device shown in FIGS. 1A and 1B includes a substrate 1, a base film 2 on the substrate 1, a conductive film 3 on the base film 2, an insulating film 4 on the conductive film 3, and a conductor on the insulating film 4.
  • the film 5 and the conductive film 6 and the insulating film 4, the conductive film 5 and the organic semiconductor film 7 on the conductive film 6 are included.
  • the semiconductor device functions as a transistor.
  • the conductive film 3 functions as a gate
  • the conductive film 5 functions as one of the source and the drain
  • the conductive film 6 functions as the other of the source and the drain.
  • the conductive films 5 and 6 are arranged separately from each other in the layer on the insulating film 4 and under the organic semiconductor film 7.
  • the conductive film 5 includes a portion extending from left to right on the paper surface of FIGS. 1A and 2. Further, the conductive film 6 extends so as to surround the right end of the conductive film 5 on the paper surface of FIGS. 1A and 2.
  • the conductive film 5 extends along the first direction
  • the conductive film 6 has a first portion 6-1 located in the first direction as viewed from the conductive film 5, and the conductive film 5 and the first.
  • the second portion 6-2 located in the second direction orthogonal to the first direction and the third located in the third direction opposite to the second direction when viewed from the region 8-1 between the portions 6-1.
  • the fourth part 6-3 and the third part 6-3 which are located in the fourth direction opposite to the first direction when viewed from the second part 6-3 and the second part 6-2. Includes a fifth portion 6-5 located in the direction.
  • the shape of the conductive film 6 shown in FIGS. 1A and 2 can be expressed as a "U" shape.
  • the conductive film 6 extends in the direction in which the conductive film 5 extends, that is, the upper portion and the lower portion extending along the first and fourth directions described above, and the conductive film 5 extends. It consists of a direction orthogonal to the direction, that is, an intermediate portion extending along the second and third directions described above. Then, typically, the end on the first direction side of the upper portion and the end on the second direction side of the intermediate portion are continuous, and the end on the first direction side of the lower portion and the end on the third direction side of the intermediate portion. The ends are continuous.
  • the intermediate portion includes the first portion 6-1 shown in FIGS. 1A and 2.
  • the upper portion also includes a second portion 6-2 and a fourth portion 6-4 shown in FIGS. 1A and 2.
  • the lower portion also includes the third portion 6-3 and the fifth portion 6-5 shown in FIGS. 1A and 2.
  • the conductive film 6 is arranged so that at least a part of the conductive film 5 is located between the upper portion and the lower portion.
  • FIGS. 3A and 3B are diagrams showing another example of the semiconductor device according to one aspect of the present invention. .. Specifically, FIG. 3A is a top view of the semiconductor device, and FIG. 3B is a cross-sectional view taken along the line segment BB'of FIG. 3A. Further, FIG. 4 is a top view showing a state in which the organic semiconductor film 25 is removed from the semiconductor device shown in FIG. 3A.
  • the semiconductor device shown in FIGS. 3A and 3B includes a base 11, a base film 13 on the base 11, a conductive film 15 on the base film 13, an insulating film 17 on the conductive film 15, and a conductive film on the insulating film 17. It includes films 19, 21 and 23, and an insulating film 17 and an organic semiconductor film 25 on the conductive films 19, 21 and 23. Then, the semiconductor device functions as a transistor. Specifically, the conductive film 15 functions as a gate, the conductive film 19 functions as one of the source and the drain, and the conductive film 21 functions as the other of the source and the drain.
  • the conductive films 19, 21 and 23 are arranged separately from each other in the layer on the insulating film 17 and under the organic semiconductor film 25.
  • the conductive films 19 and 21 include portions extending substantially in parallel from left to right on the paper surface of FIGS. 3A and 4. Further, the conductive film 23 extends so as to surround the right end of the conductive films 19 and 21 on the paper surface of FIGS. 3A and 4. In other words, the conductive films 19 and 21 extend substantially in parallel along the first direction, and the conductive film 23 is the first portion 23-1 located in the first direction when viewed from the conductive films 19 and 21.
  • a third part 23-3 located in a certain third direction
  • a fourth part 23-4 located in the fourth direction opposite to the first direction when viewed from the second part 23-2
  • a third part Includes a fifth portion 23-5 located in the fourth direction as viewed from 23-3.
  • the shape of the conductive film 23 shown in FIGS. 3A and 4 can be expressed as a "U" shape like the conductive film 6 shown in FIGS. 1A and 2.
  • the insulating films 4 and 17 are the main components of a solution containing the materials constituting the organic semiconductor films 7 and 25 as solutes.
  • An insulating film having a liquid-repellent property to a certain solvent is applied, and a conductive film having a liquid-similar property to the solvent is applied as the conductive films 5, 6, 19 and 21 and the conductive film 23 which function as a source and a drain. ing. That is, the surface free energy of the insulating films 4 and 17 is smaller than the surface free energy of the conductive films 5, 6, 19, 21 and 23. Therefore, the contact angle of the solvent with respect to the insulating films 4 and 17 is larger than the contact angle of the solvent with respect to the conductive films 5, 6, 19, 21 and 23, respectively.
  • the shapes of the conductive films 6 and 23 are not limited to the shapes shown in FIGS. 1A, 2, 3A and 4. However, the insulating film 4 in the region between the conductive film 5 and the conductive film 6 (see FIGS. 1A and 2) or the region between the conductive film 19 and the conductive film 21 (see FIGS. 3A and 4), which is the channel forming region of the thin film transistor. Alternatively, in order to form the organic semiconductor film 7 or 25 on 17, it is necessary to form a film having the following shape.
  • the solution containing the material constituting the organic semiconductor film 7 or 25 as a solute is prepared from right to left on the papers of FIGS. 1A, 2, 3A and 4. It is applied towards, i.e., along the fourth direction described above.
  • the insulating films 4 and 17 have liquid repellency to the solvent which is the main component of the solution
  • the conductive films 6 and 23 have liquor property to the solvent. It will be started when the conductive films 6 and 23 come into contact with the solution.
  • the start of coating means that the solution to be coated begins to remain on the object to be coated separately and independently from the coating members such as blades and rollers.
  • the solution is applied to a region between the conductive film 5 and the conductive film 6 (see FIGS. 1A and 2) or a region between the conductive film 19 and the conductive film 21 (FIGS. 3A and 4), which is a channel forming region of the thin film transistor. It must be started before the insulating film 4 or 17 in (see) comes into contact with the solution. Therefore, the conductive film 6 needs to be formed into a shape including the portion existing in the first direction (for example, the first portion 6-1) when viewed from the conductive film 5. Similarly, the conductive film 23 needs to be formed into a shape including the portion existing in the first direction (for example, the first portion 23-1) when viewed from the conductive film 19 and the conductive film 21. be.
  • the material constituting the organic semiconductor films 7 and 25 contained as a solute in the solution is placed between the conductive film 5 and the conductive film 6 in the coating direction thereof. Precipitated in the region (region 8-1 shown in FIGS. 1A and 2) or the region between the conductive films 19 and 21 in the coating direction thereof and the conductive film 23 (region 30-1 shown in FIGS. 3A and 4). Need to remain. In other words, in the manufacturing process, it is prevented that the solution is repelled from the regions 6-1 and 30-1 in the direction orthogonal to the direction in which the solution is applied, that is, in the above-mentioned second and third directions. There is a need to.
  • the conductive film 6 includes the portions (for example, the second portion 6-2 and the third portion 6-3) existing in the above-mentioned second direction and the third direction when viewed from the region 8-1. It is necessary to form a film so that at least a part of the portion extends continuously from the portion existing in the first direction (for example, the first portion 6-1).
  • the conductive film 23 includes portions (for example, second portion 23-2 and third portion 23-3) existing in the above-mentioned second and third directions when viewed from the region 30-1. It is necessary to form a film so that at least a part of the portion extends continuously from the portion existing in the first direction (for example, the first portion 23-1).
  • the conductive film 5 and the conductive film 6 in a direction in which the materials constituting the organic semiconductor films 7 and 25 contained as solutes in the solution are orthogonal to the coating direction thereof.
  • the conductive film 6 is formed into a shape including a portion (for example, a fourth portion 6-4 and a fifth portion 6-5) that overlaps with the conductive film 5 in the above-mentioned second and third directions. Need to be done.
  • the conductive film 23 has a shape that includes portions (for example, fourth portion 23-4 and fifth portion 23-5) that overlap with the conductive films 19 and 21 in the second and third directions described above. Needs to be filmed.
  • the conductive films 3, 5 and 6 are electrically connected to other circuit elements (transistors, signal lines, power supply lines, etc.).
  • the conductive films 15, 19 and 21 are electrically connected to other circuit elements.
  • the conductive film 23 shown in FIGS. 3A, 3B and 4 is not connected to other circuit elements, that is, is electrically isolated.
  • Bases 1 and 11 As the substrates 1 and 11, low heat resistant plastic substrates such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET) or polypropylene, or highly heat resistant plastic substrates such as polycarbonate, silicon substrates, glass substrates and the like are applied. Can be done. When a flexible substrate such as a plastic substrate is applied as the substrates 1 and 11, it is preferable because the entire semiconductor device can be made flexible. Further, as the substrates 1 and 11, pulp substrates impregnated with a fluororesin may be applied.
  • PEN polyethylene naphthalate
  • PET polyethylene terephthalate
  • highly heat resistant plastic substrates such as polycarbonate, silicon substrates, glass substrates and the like are applied.
  • a flexible substrate such as a plastic substrate is applied as the substrates 1 and 11
  • pulp substrates impregnated with a fluororesin may be applied.
  • the base films 2 and 13 and the insulating films 4 and 17 may contain a fluororesin. Further, the base films 2 and 13 and the insulating films 4 and 17 may be made of a fluororesin. The surfaces of the base films 2 and 13 and the insulating films 4 and 17 are preferably smooth surfaces without irregularities. Further, the undercoat films 2 and 13 and the insulating films 4 and 17 in one aspect of the present invention need to generate photochemical reaction radicals by irradiating with ultraviolet rays (details will be described later). Therefore, it is preferable to apply a polymer insulating material such as a fluororesin that generates reactive radicals as the base films 2 and 13 and the insulating films 4 and 17.
  • a polymer insulating material such as a fluororesin that generates reactive radicals as the base films 2 and 13 and the insulating films 4 and 17.
  • fluororesin examples include polychlorotrifluoroethylene, polyvinylfluoride, ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride, perfluoroethylene propene copolymer, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, and the like.
  • fluororesin examples include perfluoroalkoxyalkane and a fluororesin having a perfluoroalkyl ether ring structure.
  • a perfluoro resin particularly a fluororesin having a perfluoroalkyl ether ring structure
  • a perfluoro resin particularly a fluororesin having a perfluoroalkyl ether ring structure
  • a transistor having excellent characteristics can be obtained.
  • a perfluoro (3 butenyl vinyl ether) polymer (CYTOP (registered trademark) manufactured by AGC) or a perfluorodimethyldioxol-tetrafluoroethylene copolymer (Teflon (registered trademark) AF)
  • CYTOP registered trademark
  • Teflon registered trademark
  • AF perfluorodimethyldioxol-tetrafluoroethylene copolymer
  • the conductive films 3, 5, 6, 15, 19, 21 and 23 may contain a metal or an alloy containing the same, a conductive organic substance, or an organic substance in which metal nanoparticles are dispersed. Further, the conductive films 3, 5, 6, 15, 19, 21 and 23 may be made of a metal or an alloy containing the same, a conductive organic substance, or an organic substance in which metal nanoparticles are dispersed. Further, the conductive films 5 and 6 shown in FIGS. 1A and 1B and 2 may be made of the same material. Further, the conductive films 19, 21 and 23 shown in FIGS. 3A and 3B and 4 may be made of the same material. In this case, the conductive films 5 and 6 or the conductive films 19, 21 and 23 can be formed at the same time, which is preferable.
  • Examples of metals contained in conductive films 3, 5, 6, 15, 19, 21 and 23 or alloys containing them include platinum, gold, silver, aluminum, chromium, tungsten, copper, iron, lead, titanium and indium. And the like and alloys containing them (In ⁇ 2 , ZnO 2 , and indium tin oxide (ITO), etc.) and the like.
  • Examples of the conductive organic substances contained in the conductive films 3, 5, 6, 15, 19, 21 and 23 include conductive polymer compounds such as polythiophene, polyacetylene and polyparaphenylene vinylene, carbon nanotubes and graphene.
  • Examples of organic substances in which metal nanoparticles contained in conductive films 3, 5, 6, 15, 19, 21 and 23 are dispersed include tetrachloromethane, benzene, dichlorobenzene, dichloromethane, toluene, octane, tetralin and mesitylene. , Butanol, methanol and the like.
  • metal nanoparticles dispersed in the organic substance include metal nanoparticles containing gold, silver or copper as a main component and other metal elements.
  • the metal nanoparticles have a size generally called nano size (less than 1 ⁇ m), and the average particle size is preferably 10 nm or more and 100 nm or less, more preferably 30 nm or less. Further, when the metal nanoparticles contain gold or silver, the conductivity of the obtained electrode film is high, which is preferable.
  • the ratio of the metal nanoparticles is preferably 30% or more and 60% or less in terms of weight% with respect to the total mass of the material.
  • the metal nanoparticles may be coated with an organic molecular layer containing an alkylamine, an alkyldiamine, or an amine having another structure. It is considered that this coated portion is formed by bonding a large number of alkylamine molecules to metal nanoparticles by coordination bonds of amino groups and aggregating the alkyl group portions on the surface of the metal nanoparticles. Therefore, the weight ratio of the coated portion can be adjusted by adjusting the molecular weight of the alkylamine mainly used.
  • organic molecular layers containing alkylamines, alkyldiamines, or amines having other structures that coat metal nanoparticles include the following.
  • medium- and short-chain alkylamines are not particularly limited in their structure, but are RNH 2 (R is a hydrocarbon chain) which is a primary amino group or R 1 R 2 NH (R 1 , R) which is a secondary amino group. 2 is a hydrocarbon chain and may be the same or different). Further, the medium- and short-chain alkylamine has a boiling point of 100 ° C. or higher in consideration of the thermal decomposition temperature of the complex compound, and 250 ° C. or lower in consideration of the low-temperature sinterability of the coated metal nanoparticles. Is considered to be the boiling point of.
  • 2-ethoxyethylamine, dipropylamine, dibutylamine, hexylamine, cyclohexylamine, heptylamine, 3-butoxypropylamine, octylamine, nonylamine, decylamine, 3-aminopropyltriethoxysilane, dodecylamine and the like can be mentioned. However, it is not limited to these.
  • long-chain and medium-chain alkylamines examples include dipropylamine, dibutylamine, hexylamine, cyclohexylamine, heptylamine, 3-butoxypropylamine, octylamine, nonylamine, decylamine, 3-aminopropyltriethoxysilane, and the like.
  • Alkyl amines such as dodecylamine, hexadecylamine, oleylamine, and octadecylamine. Any long-chain or medium-chain alkylamine having 6 or more carbon atoms can be appropriately used depending on the intended purpose.
  • short-chain alkylamine examples include amylamine, 2-ethoxyethylamine, 4-methoxybutylamine, diisopropylamine, butylamine, diethylamine, propylamine, isopropylamine, ethylamine, dimethylamine and the like.
  • the structure of the medium- and short-chain alkyldiamine is not particularly limited, but at least one amino group is RNH 2 (R is a hydrocarbon chain) or a secondary amino group, R 1 R 2. It is desirable that it is NH (R 1 and R 2 may be the same or different in the hydrocarbon chain).
  • the medium- and short-chain alkyldiamine has a boiling point of 100 ° C. or higher in consideration of the thermal decomposition temperature of the complex compound, and a boiling point of 250 ° C. or lower in consideration of the low-temperature sinterability of the coated metal nanoparticles. Is considered.
  • the organic semiconductor films 7 and 25 may include one or both of a high molecular weight organic semiconductor material and a low molecular weight organic semiconductor material.
  • the polymer means a molecule having a molecular weight of more than 10,000
  • the small molecule means a molecule having a molecular weight of 10,000 or less.
  • the organic semiconductor material constituting the organic semiconductor films 7 and 25 is preferably a small molecule organic semiconductor material.
  • the molecular weight of the small molecule organic semiconductor material is preferably 1500 or less, more preferably 800 or less.
  • the molecular skeleton of the organic semiconductor material is not particularly limited as long as it has semiconductor performance.
  • a condensed polycyclic aromatic compound is preferable, a condensed polycyclic aromatic compound having an acene skeleton or a heteroacene skeleton is more preferable, and a condensed polycyclic having a thienoacene skeleton is more preferable.
  • Aromatic compounds are particularly preferable, and compounds represented by the following formula (2) or (3) are most preferable.
  • the organic semiconductor material is dissolved in an organic solvent when the organic semiconductor films 7 and 25 are formed, it is preferable that the organic semiconductor material has solvent solubility.
  • the organic semiconductor material has an alkyl group in order to ensure solubility.
  • the thienoacene skeleton refers to a compound containing at least one thiophene ring structure represented by the following formula (1) as a condensed ring site in the molecular structure.
  • R1 represents an alkyl group.
  • R2 represents an aromatic hydrocarbon group which may have an alkyl group or a heterocyclic group which may have an alkyl group.
  • R3 and R5 are hydrogen atoms
  • one of R4 and R6 has an alkyl group, and the other has an aromatic hydrocarbon group or an alkyl group which may have an alkyl group.
  • the formula (3) when any three of R3 to R6 are hydrogen atoms, the remaining one represents an alkyl group.
  • alkyl groups are not limited to straight chain, branched chain and cyclic.
  • examples of these alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group and n-. Dodecyl group, 2-ethylhexyl group and the like can be mentioned.
  • a linear alkyl group is preferable, a linear alkyl group having 4 to 14 carbon atoms is more preferable, a linear alkyl group having 6 to 12 carbon atoms is further preferable, and a linear alkyl group having 8 to 12 carbon atoms is more preferable.
  • a straight chain alkyl group is most preferred.
  • the aromatic hydrocarbon group which may have an alkyl group means a functional group in which one of the hydrogen atoms on the aromatic hydrocarbon is substituted with an alkyl group, and specific examples thereof include a phenyl group and a naphthyl group. , Anthrill group and the like.
  • a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • the heterocyclic group which may have an alkyl group represents a similar mode in which the aromatic hydrocarbon group is replaced with the heterocyclic group.
  • the heterocyclic group include a pyridyl group, a pyrazil group, a pyrimidyl group, an imidazolyl group, a thienyl group, a benzothienyl group and the like.
  • a preferable heterocyclic group includes a thienyl group or a benzothienyl group.
  • Examples of the polymer organic semiconductor material constituting the organic semiconductor films 7 and 25 include polythiophene, polyphenylene vinylene, polyfluorene, polyacetylene, polypyrrole, etc., as well as monomers having high electron density such as benzodithiophene and thienothiophene, and benzothiasiasol. , Benzobistianiazole, diketopyrrolopyrrole and other donor-acceptor-type polymers obtained by copolymerizing monomers with low electron density.
  • Two or more materials may be mixed and used as an organic semiconductor material constituting the organic semiconductor films 7 and 25 for the purpose of improving the characteristics of the semiconductor device or imparting other characteristics.
  • the organic semiconductor material to be mixed may be either a high molecular weight organic semiconductor material or a low molecular weight organic semiconductor material.
  • the higher the crystallinity of the semiconductor film the better the characteristics of the thin film transistor.
  • Adv. Mater. 2018.30.1072756 describes that an organic semiconductor film having high crystallinity can be obtained by using a mixture of two kinds of small molecule organic semiconductor materials. Therefore, when the organic semiconductor films 7 and 25 are formed using an organic semiconductor material in which two or more materials are mixed, it is preferable that both of the two materials are low molecule organic semiconductor materials. Further, it is more preferable that the two materials are small molecule organic semiconductors having the same molecular structure and different alkyl group lengths.
  • these materials may be dispersed in an organic substance as a solvent. That is, the organic semiconductor films 7 and 25 may be made of an organic substance in which these materials are dispersed. Further, the organic semiconductor films 7 and 25 may contain additives.
  • the additives contained in the organic semiconductor films 7 and 25 are not particularly limited as long as they do not interfere with the function of the semiconductor device.
  • examples of such additives include insulating materials, surfactants or thickeners for rheology control, carrier injection or dopants for adjusting the amount of carriers, and the like.
  • the organic substance that serves as a solvent for these materials can be used without particular limitation as long as it can dissolve and disperse these materials, but when storage stability is taken into consideration, it must be a solvent that can dissolve the materials. Is desirable.
  • the organic substances include halogen-based solvents such as chloroform, chlorobenzene and dichlorobenzene, aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, mesitylene, tetraline and cyclohexylbenzene, and ethers such as tetrahydrofuran, anisole and phenetol.
  • Amids such as dimethylformamide and dimethylacetamide, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone, esters such as methyl benzoate and ethyl benzoate, and hydrocarbons such as cyclohexane and decalin Can be mentioned.
  • FIGS. 5A to 5D are diagrams showing an example of the manufacturing method of the semiconductor device shown in FIGS. 1A, 1B and 2, and specifically, the base film 2 is manufactured on the substrate 1. It is a figure which shows from the film (FIG. 5A) to the film formation of the conductive film 5 and 6 (FIG. 5D) in the order of film formation.
  • FIGS. 5A to 5D show an example of a method for manufacturing the semiconductor device shown in FIGS. 1A, 1B and 2, the semiconductor device shown in FIGS. 3A, 3B and 4 can be manufactured by the same manufacturing method. Is also possible.
  • a solution containing the material constituting the base film 2 as a solute is applied onto the substrate 1.
  • a spin coating method, a dip coating method, a spray coating method, a droplet ejection method, a die coating method and the like can be applied.
  • the applied solution may be heat-treated at a temperature of 200 ° C. or lower, or may be naturally dried. As a result, the formation of the base film 2 on the substrate 1 is completed (see FIG. 5A).
  • the base film 2 in the region where the conductive film 3 is later formed is selectively irradiated with ultraviolet rays.
  • a method of irradiating ultraviolet rays a method of irradiating the entire surface of the base film 2 with ultraviolet rays while covering a region other than the first pattern region with a photomask, a method of irradiating only the first pattern region with an ultraviolet laser, and the like can be applied. can.
  • the surface of the base film 2 in the first pattern region becomes a reactive surface by a photochemical reaction.
  • the reactive surface means that radical groups are generated on the insulating film surface by a photochemical reaction of an insulating film such as a perfluoro resin due to ultraviolet irradiation, and organic substances in which metal nanoparticles are dispersed adhere and aggregate. A surface that is in an easy-to-use state.
  • the radical group promotes the detachment of the organic molecular layer and the metal nanoparticles adhere to each other.
  • Aggregation fusion / aggregation
  • adhesion / agglutination or fusion / aggregation means a state in which metal nanoparticles are adhered (fused) to a film to be formed and aggregated.
  • the ultraviolet rays irradiated to the base film 2 are irradiated for the purpose of dissociating the bond between carbon (C) and fluorine (F) in the base film 2.
  • the binding energy of carbon (C) and fluorine (F) is about 490 kJ / mol. Therefore, if the wavelength of the ultraviolet rays is 244 nm or less, it is considered that the bond between carbon (C) and fluorine (F) can be dissociated.
  • the wavelength of the ultraviolet rays may be 10 nm to 244 nm, preferably 10 nm to 200 nm, and more preferably 100 nm to 200 nm.
  • a solution containing the material constituting the conductive film 3 as a solute is applied onto the undercoat film 2.
  • a method of applying the solution a method using an application member such as a blade and a roller can be applied.
  • a method of dropping the solution onto the base film 2 and applying the solution to the first pattern region of the base film 2 by sweeping a blade close to the base film 2 or rotating a roller can be applied. ..
  • the solution 150 is dropped onto the base film 2, and the blade 200 adjacent to the base film 2 is swept from right to left on the paper surface to bring the solution 150 to the base film 13. It may be applied to one pattern area.
  • the direction in which the blade 200 is swept may be any direction.
  • a solution containing the material constituting the conductive film 3 as a solute is applied only to the first pattern region. Then, the applied solution may be heat-treated at a temperature of 200 ° C. or lower, or may be naturally dried. With the above, the film formation of the conductive film 3 is completed (see FIG. 5B). Regarding the formation of the conductive film 3 on the base film 2, the disclosure contents of JP-A-2014-195794 may be referred to.
  • a solution containing the material constituting the insulating film 4 as a solute is applied onto the base film 2 and the conductive film 3.
  • a method for applying the solution the same method as the method for applying the solution containing the material constituting the base film 2 as a solute can be adopted, and therefore the above description is incorporated.
  • the applied solution may be heat-treated at a temperature of 200 ° C. or lower, or may be naturally dried. With the above, the film formation of the insulating film 4 is completed (see FIG. 5C).
  • the insulating film 4 in the region where the conductive films 5 and 6 are formed is selectively irradiated with ultraviolet rays.
  • the method of irradiating the ultraviolet rays the same method as the method of irradiating the base film 2 with ultraviolet rays can be adopted, and therefore the above description is incorporated.
  • a solution containing the materials constituting the conductive films 5 and 6 as a solute is applied onto the insulating film 4.
  • a method for applying the solution the same method as the method for applying the solution containing the material constituting the conductive film 3 as a solute can be adopted, and therefore the above description is incorporated.
  • a solution containing the materials constituting the conductive films 5 and 6 as a solute is applied only to the second pattern region. Then, the applied solution may be heat-treated at a temperature of 200 ° C. or lower, or may be naturally dried. Further, the conductive films 5 and 6 may be surface-treated.
  • An example of the surface treatment is a surface treatment using benzenethiol in which at least one hydrogen atom is replaced with a fluorine atom.
  • the liquid friendliness of the surfaces of the conductive films 5 and 6 with respect to the solvent which is the main component of the solution containing the material constituting the organic semiconductor film 7 as a solute is improved.
  • the film formation of the conductive films 5 and 6 is completed (see FIG. 5D).
  • the disclosure contents of JP-A-2014-195794 may be referred to.
  • a solution containing the material constituting the organic semiconductor film 7 as a solute is applied onto the conductive films 5 and 6 and the insulating film 4.
  • a method for applying the solution the same method as the method for applying the solution containing the materials constituting the conductive films 3, 5 and 6 as a solute can be adopted.
  • the application of the solution containing the material constituting the organic semiconductor film 7 as a solute is performed along a specific direction.
  • FIGS. 7A and 7B to 11A and 11B An example of a method for applying a solution containing a material constituting the organic semiconductor film 7 as a solute will be described in detail with reference to FIGS. 7A and 7B to 11A and 11B.
  • 7A to 11A are top views showing changes when the solution is applied
  • FIGS. 7B to 11B are cross-sectional views taken along the line CC'shown in FIGS. 7A to 11A.
  • a solution 250 containing the material constituting the organic semiconductor film 7 as a solute is dropped onto the insulating film 4 located in the direction opposite to the side where the conductive film 5 is located when viewed from the conductive film 6. Then, as shown in FIGS. 7A and 7B, the blade 300 is placed at a position where it comes into contact with the solution 250 and does not come into contact with the insulating film 4 or the like.
  • the blade 300 preferably has liquid repellency against the solution 250.
  • the surface of the blade 300 is liquid-repellent so as to have liquid-repellent property against the solution 250.
  • a perfluoro (3 butenyl vinyl ether) polymer (CYTOP (registered trademark) manufactured by AGC Inc.) or a perfluorodimethyldioki, which is a suitable material for the insulating film 4, is used.
  • Processing using a sole-tetrafluoroethylene copolymer (Teflon (registered trademark) AF) or the like can be mentioned.
  • the blade 300 is swept in the direction of the arrow shown in FIG. 7A, that is, from right to left on the paper surface. In other words, the blade 300 is swept along the fourth direction described above.
  • the solution 250 When the solution 250 also moves to the conductive film 6 side with the movement of the blade 300, the solution 250 is located on the conductive film 6 as shown in FIGS. 8A and 8B.
  • the rear end of the solution 250 (the right end on the paper surface of FIGS. 8A and 8B) follows the movement of the blade 300. It is stretched without. Further, at the rear end of the solution 250, drying (volatilization of the solvent) is promoted. As a result, the organic semiconductor material which is the solute of the solution 250 is precipitated, so that the formation of the organic semiconductor film 7 on the conductive film 6 is started.
  • the rear portion of the solution 250 (the right portion on the paper in FIGS. 9A and 9B) is already present. It is stretched by the formed organic semiconductor film 7. Further, due to the presence of the conductive film 6 having positivity in the rear and left and right of the rear portion, the rear portion is repelled without being separated from the organic semiconductor film 7 formed on the conductive film 6. It is also located on the liquid insulating film 4. Then, drying (solvent volatilization) is promoted also in the rear portion located in the insulating film 4.
  • the organic semiconductor material which is the solute of the solution 250 is precipitated, so that the organic semiconductor film 7 is also formed on the conductive film 4.
  • the insulating film 4 on the side opposite to the side where the conductive film 5 is located when viewed from the conductive film 6 does not have a structure for stretching a part of the solution 250, so that the drying of the solution 250 is promoted. Therefore, the organic semiconductor film 7 is not formed.
  • the above-mentioned semiconductor device and its manufacturing method are examples of the present invention, and the present invention also includes a semiconductor device having features different from those of the above-mentioned semiconductor device and its manufacturing method and its manufacturing method.
  • the base films 2 and 13 shown in FIGS. 1B and 3B are not indispensable configurations in the present invention. Therefore, as shown in FIG. 12, a semiconductor device in which the substrate 1 is in contact with the conductive film 3 and the insulating film 4 is also an aspect of the present invention. Since the semiconductor device shown in FIG. 1B or the like is formed by the above-mentioned manufacturing method, it is preferable in that the conductive film 3 can be patterned with high definition by a relatively simple method. On the other hand, the semiconductor device shown in FIG. 12 is preferable in that the film forming process of the base film 2 can be reduced.
  • the shape of the conductive film on which the organic semiconductor film is first formed is "co". It is not limited to the shape of.
  • the shape of the conductive film any of the shapes of the conductive films 23 ′′ to 23 ′′ shown in FIGS. 13 to 15 can be applied.
  • FIGS. 13 to 15 show modified examples of the conductive film 23 shown in FIGS. 3A and 3B
  • the shape of the conductive film 7 shown in FIGS. 1A and 1B is shown in FIGS. 13 to 15. It can also be changed to a shape of' ⁇ 23'''.
  • the conductive film 23' refers to the direction in which the conductive films 19 and 21 extend, that is, the upper portion and the lower portion extending along the first direction and the fourth direction, and the upper portion. It consists of an intermediate portion that curves and extends from the end on the unidirectional side to the end on the first direction side of the lower portion.
  • the conductive film 23' is the same as the conductive film 23 shown in FIGS. 3A and 4, the first portion 23'-1 located in the first direction and the conductive film when viewed from the conductive films 19 and 21. Seen from the region between 19 and 21 and the first portion 23'-1, the second portion 23'-2 located in the second direction and the third portion 23'-3 located in the third direction described above. And the fourth part 23'-4 located in the fourth direction when viewed from the second part 23'-2, and the fourth part located in the fourth direction when viewed from the third part 23'-3. Includes 5 parts 23'-5 and.
  • the upper portion of the conductive film 23' includes a part of the second portion 23'-2 and the fourth portion 23'-4. Further, the lower portion of the conductive film 23'includes a part of the third portion 23'-3 and the fifth portion 23'-5. Further, the intermediate portion of the conductive film 23'includes the first portion 23'-1, the rest of the second portion 23'-2, and the third portion 23'-3.
  • the conductive film from which the organic semiconductor film is first formed in the semiconductor device of the present invention may include a plurality of separated sub-conductive films 23A to 23C.
  • the sub-conductive film 23A includes the portion 23 ′′ -1 located in the first direction as viewed from the conductive films 19 and 21.
  • the sub-conductive film 23B includes a part located in the second direction when viewed from the region between the conductive films 19 and 21 and the portion 23''-1, and the above-mentioned first film when viewed from the conductive film 19. It consists of the rest located in two directions.
  • the sub-conductive film 23C is a part located in the third direction when viewed from the region between the conductive films 19 and 21 and the portion 23 ′′ -1, and the above-mentioned first film when viewed from the conductive film 21. It consists of the rest located in three directions. Further, the sub-conductive film 23A is viewed from the portion of the sub-conductive film 23B located in the second direction when viewed from the end of the sub-conductive film 23B on the first direction side and the end of the sub-conductive film 23C on the first direction side. As seen, it includes the portion located in the third direction described above.
  • the sub-conductive films 23A to 23C shown in FIG. 14 are the first portion 23 located in the first direction described above when viewed from the conductive films 19 and 21 in the same manner as the conductive films 23 shown in FIGS. 3A and 4.
  • the second portion 23''-2 located in the second direction and the third direction described above when viewed from the region between''-1 and the conductive films 19 and 21 and the first portion 23''-1.
  • the third part 23''-3 located in the above, the fourth part 23''-4 located in the fourth direction as viewed from the second part 23''-2, and the third part 23''- Seen from 3, the fifth portion 23''-5 located in the fourth direction described above is included.
  • the first portion 23 ′′ -1 in the sub-conductive films 23A to 23C shown in FIG. 14 includes a part of the sub-conductive film 23A.
  • the second portion 23 ′′ -2 in the sub-conductors 23A to 23C shown in FIG. 14 includes a part of the sub-conductive film 23A and a part of the sub-conductive film 23B.
  • the end of the sub-conductive film 23B extends in the first direction at a position shifted in the third direction (lower part of the figure) from the upper end of the sub-conductive film 23A. Therefore, it is preferable that there is a region where a part of the sub-conductive film 23A and a part of the sub-conductive film 23B overlap in the first direction.
  • the third portion 23 ′′ -3 in the sub-conductive film 23A to 23C shown in FIG. 14 includes a part of the sub-conductive film 23A and a part of the sub-conductive film 23C.
  • the end of the sub-conductive film 23C extends in the first direction at a position deviated from the lower end of the sub-conductive film 23A in the second direction (upper part of the drawing). Therefore, it is preferable that there is a region where a part of the sub-conductive film 23A and a part of the sub-conductive film 23C overlap in the first direction.
  • the fourth portion 23 ′′ -4 in the sub-conductive films 23A to 23C shown in FIG. 14 includes the remainder of the sub-conductive film 23B.
  • the fifth portion 23 ′′ -5 in the sub-conductive films 23A to 23C shown in FIG. 14 includes the remainder of the sub-conductive film 23C.
  • the conductive film from which the organic semiconductor film is first formed is composed of three sub-conductive films 23A to 23C, but the number of sub-conductive films may be 2 or 4 or more. ..
  • at least one of the first to fifth portions includes at least a part of each of at least two sub-conductives among the plurality of subconductives.
  • the conductive film from which the organic semiconductor film is first formed is one end portion 23 ′′ ′′ -6 and the other end portion 23, as shown in FIG. '''-7 may extend so as not to overlap with the conductive films 19 and 21 in the above-mentioned second direction and third direction.
  • the semiconductor device having the conductive film 23 shown in FIG. 4B or the like reduces the parasitic capacitance generated in the conductive films 19 and 21 as compared with the semiconductor device having the conductive film 23 ′ ′′ shown in FIG. It is preferable in that it can be used.
  • the semiconductor device having the conductive film 23'''shown in FIG. 15 has the conductive film 19 and the conductive film which are the channel forming regions of the transistor as compared with the semiconductor device having the conductive film 23 shown in FIG. It is preferable in that the organic semiconductor film 25 can be reliably formed in the region between 21.
  • the undercoat film 2 or 13 and the conductive film 3 or 15 may be formed by using a known photolithography step.
  • the conductive film 3 or 15 can be patterned with high definition by a relatively simple method, which is preferable.
  • a known photolithography process when a known photolithography process is used, the degree of freedom in material selection and the like is increased, that is, it is possible to select a material suitable for each from a wider range of options, which is preferable.
  • the conductive films 5 and 6 or the conductive films 19, the films 21 and 23 may be formed by the same step or may be formed by different steps. When these are formed in the same process, it is preferable in that the film forming process of the semiconductor device can be reduced. On the other hand, when these are formed by different steps, the degree of freedom in material selection is increased, which is preferable.
  • a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was manufactured . ..
  • a silicon wafer with a SiO 2 thermal oxide film (100 nm) is prepared as a substrate, and CYTOP CTL809M (registered trademark) manufactured by AGC Inc., which serves as a base film, is spin-coated on the substrate so as to have a thickness of about 25 nm. The film was applied and formed.
  • gold (Au) which is a material for the conductive film
  • Au gold
  • the obtained solution was blade-coated on the above-mentioned substrate at a rate of 3.5 ⁇ m / sec using a glass blade, and dried at room temperature to form an organic semiconductor in which a semiconductor film was formed only where necessary.
  • the glass blade is coated with CYTOP CTL809M (registered trademark) manufactured by AGC Inc.
  • the film thickness of the obtained organic semiconductor film was about 5 nm.
  • FIG. 16 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope.
  • the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, it was found that the organic semiconductor film was formed on the CYTOP outside the region shown by the dotted line in the figure. No blinking of the indicated color was observed, and it was confirmed that the organic semiconductor film was not formed.
  • the region surrounded by the conductive film shown by the dotted line it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.
  • Example 1 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 800 ⁇ m and a channel length of 100 ⁇ m included in the semiconductor device manufactured in Example 1 were measured.
  • SiO 2 as a thermal oxide film layer and CYTOP CTL809M (registered trademark) manufactured by AGC Inc. as an undercoat film serve as an insulating film, and the capacitance is 24 nF / cm 2 and the element characteristic value is set. Calculated.
  • the output characteristics of the organic thin film transistor element included in the obtained semiconductor device are shown in FIG. As shown in FIG.
  • the organic thin film transistor element exhibited linear and saturated output characteristics similar to a typical transistor element. Further, as shown in FIG. 18, the thin film transistor was capable of being driven at a low voltage of 2 V or less and had a small hysteresis. When the sub-threshold swing value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 67 mV / dec, showing an extremely steep switching characteristic approaching the theoretical limit. Moreover, when the carrier mobility of the organic thin film transistor element was calculated, it showed a high mobility of 4.4 cm 2 / Vs at the maximum.
  • the semiconductor device was manufactured by the same method as that described in 1.
  • a polarizing microscope photograph of the obtained semiconductor device is shown in FIG.
  • the organic semiconductor was crystalline only in the region surrounded by the conductive film shown by the dotted line in the figure. The result was that a thin film was obtained.
  • Example 3 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 300 ⁇ m and a channel length of 50 ⁇ m included in the semiconductor device manufactured according to Example 3 were measured.
  • the insulating film and capacitance of the organic thin film transistor element are the same as those of the film and values described in Example 2.
  • the output characteristics of the organic thin film transistor element included in the obtained semiconductor device are shown in FIG. As shown in FIG. 20, the organic thin film transistor element exhibited linear and saturated output characteristics similar to a typical transistor element. Further, as shown in FIG. 21, the thin film transistor was capable of being driven at a low voltage of 2 V or less and had a small hysteresis.
  • the sub-threshold swing value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 75 mV / dec, showing an extremely steep switching characteristic.
  • the carrier mobility of the organic thin film transistor element was calculated, it showed a high mobility of 1.0 cm 2 / Vs at the maximum.
  • Example 1 Characteristics of Organic Thin Film Transistor Elements Consists of Source and Drain Electrodes with a Channel Width of 800 ⁇ m and a Channel Length of 100 ⁇ m in the Semiconductor Device Manufactured in Example 1 was evaluated.
  • the results of evaluating the mobility, subthreshold swing (SS) value, threshold voltage value required for switching transistors, and their variations when the drain voltage Vd is -0.2V and -2.0V are as follows. It is shown in Table 1. [Table 1]
  • a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B having a gate electrode, a source electrode, and a drain electrode formed by a printing process using silver nanoink was manufactured.
  • a glass substrate was prepared as a substrate, and CYTOP CTL809M (registered trademark) manufactured by AGC Inc., which was a base film, was applied and formed on the substrate by a spin coating method.
  • an ink containing silver nanoparticles described in the above-mentioned known document (Nature C Cincinnatimmun. 2016, 7, 11402-1-9) is coated with the blade coat described in the same known document.
  • a film was formed by the method to prepare a gate electrode composed of silver nanoparticles.
  • CYTOP CTL809M was coated and formed by a spin coating method in the same manner as described above, and then pentafluorobenzenethiol was vapor-phase treated in the same manner as in Example 1 and silver was treated in the same manner as described above.
  • Source electrodes, drain electrodes and guide electrodes made of nanoparticles were prepared.
  • the semiconductor layer is formed by forming the semiconductor material described in Example 1 by the same method as that described in Example 1, and forming an organic semiconductor device in which the semiconductor film is formed only at necessary locations.
  • a source and drain electrode layer composed of a CYTOP layer and silver nanoparticles was formed on a silicon substrate with an oxide film by the same method as described above.
  • a photograph of the semiconductor device obtained in FIG. 22 is shown in FIG.
  • the organic semiconductor film was formed on the CYTOP outside the region shown by the black dotted line in the figure. No blinking of the color indicating the above was observed, and it was confirmed that the organic semiconductor film was not formed. On the other hand, in the region surrounded by the conductive film shown by the dotted line, it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.
  • Example 6 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 800 ⁇ m and a channel length of 200 ⁇ m included in the semiconductor device manufactured in Example 6 were measured.
  • the capacitance of the CYTOP CTL809M layer which plays the role of an insulating film, was calculated based on the experimentally obtained value, and the device characteristic value was calculated as 2.9 nF / cm 2.
  • the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis.
  • SS sub-threshold swing
  • Example 7 In contrast to the method described in Example 1 of manufacturing a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B, manufacturing a gold electrode which is a conductive film is described in Example 7.
  • the semiconductor solution used for manufacturing the semiconductor layer is No. 1 which is the following known organic semiconductor material. 3 and No. No. 4 was dissolved in chlorobenzene so that the mass concentration was 0.05%, and then No. 3: No.
  • Manufactured semiconductor devices including.
  • FIG. 23 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope.
  • the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, the organic semiconductor film was formed on the CYTOP outside the region shown by the black dotted line in the figure. No blinking of the color indicating the above was observed, and it was confirmed that the organic semiconductor film was not formed.
  • the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.
  • Example 8 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 800 ⁇ m and a channel length of 80 ⁇ m included in the semiconductor device manufactured in Example 8 were measured.
  • SiO 2 as a thermal oxide film layer and CYTOP CTL809M as an undercoat film play the role of an insulating film, and the element characteristic value was calculated assuming that the capacitance is 2.5 nF / cm 2.
  • the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis.
  • SS sub-threshold swing
  • a semiconductor having a U-shaped electrode pattern included in the semiconductor device device manufactured by the present invention is formed by forming a film by a blade coating method. We verified whether a thin film could be formed.
  • CYTOP CTL809M which is a base film, is applied to a silicon substrate with an oxide film by a spin coating method to form a film, and then VUV light is patterned and irradiated through a photomask, and then an ink containing silver nanoparticles is formed by a blade coating method.
  • a conductive film made of silver nanoparticles was prepared.
  • a semiconductor thin film was formed on this substrate by the same method as that described in Example 8. The obtained results are shown in FIG. In the figure, the semiconductor thin film was formed only in the region indicated by the black dotted line, and it was confirmed that the semiconductor could be patterned and formed by the arrangement of the conductive film according to the present invention.
  • the semiconductor solution used for forming the semiconductor layer is a known organic semiconductor material described below. No.
  • a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was manufactured by the same method as that described in Example 1 except that the value was changed to 5.
  • FIG. 25 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope.
  • the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, the organic semiconductor film was formed on the CYTOP outside the region shown by the black dotted line in the figure. No blinking of the color indicating the above was observed, and it was confirmed that the organic semiconductor film was not formed.
  • the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.
  • Example 11 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 800 ⁇ m and a channel length of 100 ⁇ m included in the semiconductor device manufactured according to Example 11 were measured.
  • SiO 2 as a thermal oxide film layer and CYTOP CTL809M as an undercoat film play the role of an insulating film, and the element characteristic value was calculated assuming that the capacitance is 23 nF / cm 2.
  • the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis.
  • SS sub-threshold swing
  • FIG. 26 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope.
  • the pattern of the conductive film in this example is the same as that shown in FIG. 16 used in Example 1, and the photograph shown in FIG. 25 shows a source electrode portion and a drain electrode portion that function as semiconductor devices. Is an enlargement of.
  • the organic semiconductor film was formed on the CYTOP outside the region shown by the black dotted line in the figure. No blinking of the color indicating the above was observed, and it was confirmed that the organic semiconductor film was not formed.
  • the region surrounded by the conductive film shown by the dotted line it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.
  • Example 13 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 800 ⁇ m and a channel length of 200 ⁇ m included in the semiconductor device manufactured according to Example 13 were measured.
  • SiO 2 as a thermal oxide film layer and CYTOP CTL809M as an undercoat film play the role of an insulating film, and the element characteristic value was calculated assuming that the capacitance is 23 nF / cm 2.
  • the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis.
  • SS sub-threshold swing
  • a semiconductor solution used for forming a semiconductor layer is used as a commercially available organic semiconductor material.
  • the method was the same as that described in Example 1 except that the semiconductor solution was blade-coated at a rate of 5.0 ⁇ m / sec by changing to a chlorobenzene solution of a certain poly (3-hexyl) thiophene (manufactured by Merck).
  • a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was manufactured.
  • a photograph of the semiconductor device obtained by observation using a microscope is shown in FIG. 27.
  • FIG. 28 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope.
  • the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, it was found that the organic semiconductor film was formed on the CYTOP outside the region shown by the dotted line in the figure. No blinking of the indicated color was observed, and it was confirmed that the organic semiconductor film was not formed.
  • the region surrounded by the conductive film shown by the dotted line it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.
  • FIGS. 3A and 3B show a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope.
  • the value of the contact angle of the organic solvents chlorobenzene and THER-xylene used in the semiconductor solution in the examples is the insulation that is the substrate rather than the conductive film in all the combinations of the conductive film and the substrate of the semiconductor layer in the above examples.
  • the film surface showed a larger value.
  • the relationship between the water contact angles was the same as in the previous term.
  • FIGS. 3A and 3B The shape corresponding to the conductive film 23 shown in FIGS.
  • the semiconductor device was manufactured by the same method as that described in Example 1 except that the conductive film was formed so as to include only the conductive films 19 and 21 shown in FIGS. 3A and 3B.
  • FIG. 30 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope. When the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, the organic semiconductor film was formed on the CYTOP outside the region shown by the dotted line on the right side of FIG.
  • the organic semiconductor thin film was formed only on the conductive film shown by the dotted line. Therefore, it is not possible to manufacture an organic semiconductor thin film in the channel region of a semiconductor device in which one of the conductive films is a source electrode and the other is a drain electrode, and a semiconductor device cannot be manufactured.

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Abstract

Le problème à résoudre par la présente invention est de fournir un dispositif à semi-conducteur comprenant un transistor à couches minces qui peut être fabriqué plus facilement par comparaison aux procédés classiques. À cet effet, avant la formation d'un film semi-conducteur organique sur un film d'isolation qui est lyophobe par rapport à un solvant, qui est un composant principal d'une solution comprenant un matériau constituant un film semi-conducteur organique en tant que soluté, un film conducteur qui est lyophile par rapport au solvant est formé selon une forme souhaitée. Il est ainsi possible de former le film semi-conducteur organique à une position souhaitée, telle qu'une région de formation de canal du transistor à couches minces. Dans un dispositif à semi-conducteur selon un mode de réalisation de la présente invention, par exemple, des films conducteurs qui sont situés dans une couche inférieure d'un film semi-conducteur organique et au-dessus d'un film d'isolation fonctionnant comme un film d'isolation de grille, et qui fonctionnent respectivement comme une source et un drain ont des formes souhaitées.
PCT/JP2021/007036 2020-02-26 2021-02-25 Dispositif à semi-conducteur et son procédé de fabrication WO2021172408A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006060079A (ja) * 2004-08-20 2006-03-02 Ricoh Co Ltd 半導体層のパターン形成方法及び電子素子、電子素子アレイ、表示装置
JP2007300116A (ja) * 2006-04-28 2007-11-15 Samsung Electronics Co Ltd 表示装置とその製造方法
JP2009141203A (ja) * 2007-12-07 2009-06-25 Ricoh Co Ltd 有機トランジスタ、有機トランジスタアレイ及び表示装置
JP2009239033A (ja) * 2008-03-27 2009-10-15 Toppan Printing Co Ltd 有機薄膜トランジスタまたは／および有機薄膜トランジスタアレイの製造方法と有機薄膜トランジスタ、有機薄膜トランジスタアレイ
JP2013157525A (ja) * 2012-01-31 2013-08-15 Citizen Holdings Co Ltd 有機トランジスタ
US20130328049A1 (en) * 2012-06-11 2013-12-12 Samsung Display Co., Ltd. Thin-film transistor substrate and method of manufacturing the same
JP2019153653A (ja) * 2018-03-02 2019-09-12 三菱ケミカル株式会社 有機半導体装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006060079A (ja) * 2004-08-20 2006-03-02 Ricoh Co Ltd 半導体層のパターン形成方法及び電子素子、電子素子アレイ、表示装置
JP2007300116A (ja) * 2006-04-28 2007-11-15 Samsung Electronics Co Ltd 表示装置とその製造方法
JP2009141203A (ja) * 2007-12-07 2009-06-25 Ricoh Co Ltd 有機トランジスタ、有機トランジスタアレイ及び表示装置
JP2009239033A (ja) * 2008-03-27 2009-10-15 Toppan Printing Co Ltd 有機薄膜トランジスタまたは／および有機薄膜トランジスタアレイの製造方法と有機薄膜トランジスタ、有機薄膜トランジスタアレイ
JP2013157525A (ja) * 2012-01-31 2013-08-15 Citizen Holdings Co Ltd 有機トランジスタ
US20130328049A1 (en) * 2012-06-11 2013-12-12 Samsung Display Co., Ltd. Thin-film transistor substrate and method of manufacturing the same
JP2019153653A (ja) * 2018-03-02 2019-09-12 三菱ケミカル株式会社 有機半導体装置

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