WO2021172408A1 - Semiconductor device and production method therefor - Google Patents

Semiconductor device and production method therefor 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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French (fr)
Japanese (ja)
Inventor
達生 長谷川
暁 北原
井上　悟
俊人 荒井
光弘 井川
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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/en

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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 adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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 adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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 a potential-jump barrier or a surface barrier
    • 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.

Abstract

[Problem] To provide a semiconductor device including a thin-film transistor that can be more easily produced in comparison to conventional methods. [Solution] Prior to forming an organic semiconductor film upon an insulation film that is lyophobic with respect to a solvent, which is a main component of a solution including a material constituting an organic semiconductor film as a solute, a conductive film that is lyophilic with respect to the solvent is formed in a desired shape. It is thus possible to form the organic semiconductor film at a desired position, such as a channel formation region of the thin-film transistor. In a semiconductor device according to one mode of the present invention, for example, conductive films that are in a lower layer of an organic semiconductor film and above an insulation film functioning as a gate insulation film, and that respectively function as a source and a drain have desired shapes.

Description

半導体装置及びその製造方法Semiconductor devices and their manufacturing methods
　本発明の一態様は、薄膜トランジスタを含む半導体装置に関する。また、本発明の一態様は、塗布プロセスを用いる当該半導体装置の製造方法に関する。 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.
　有機半導体化合物を溶媒に溶解し、得られた溶液を塗布することによって有機半導体膜を製膜することができる。シリコン等によって構成される無機半導体膜を製膜する際には真空プロセスが必要となるのに対して、有機半導体膜は、このような真空プロセスを用いることなく製膜することが可能である。そのため、その製造コストは比較的安価である。また、製膜が行われるチャンバー内を真空に減圧する必要もないため、有機半導体膜の製膜を大型のチャンバー内において行うことも比較的容易である。そして、この場合には有機半導体膜を含む半導体素子を大面積且つ大量に製造することが可能である。加えて、有機半導体膜は、無機半導体膜を製膜する際に必要とされる高温加熱プロセスを用いることなく製膜される。そのため、有機半導体膜の製膜が行われる基体は、耐熱性の基体に限定されることなく、比較的安価なプラスチック材料からなるフレキシブル基体であってもよい。その結果、無機半導体膜を含む半導体素子を用いる場合には困難であったフレキシブルデバイスの製造も現在では可能になっている。このような状況の下、有機半導体膜を含む半導体素子及びそれを含むデバイスの研究開発が盛んに行われるようになっている。 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. Therefore, 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. As a result, it is now possible to manufacture flexible devices, which was difficult when using a semiconductor element containing an inorganic semiconductor film. Under such circumstances, research and development of semiconductor devices including organic semiconductor films and devices including them have been actively carried out.
　有機半導体膜を含む半導体素子の一例としては、有機半導体膜にチャネルが形成される薄膜トランジスタが挙げられる。このようなトランジスタの実用化に向けては、その製造工程（例えば、チャネルとして機能する箇所のみに選択的に有機半導体層を塗布する技術）及び特性（例えば、高キャリア移動度、オンからオフへのスイッチング又はその逆のスイッチングの際にヒステリシスが発生しないこと（ヒステリシスフリーであること）及び閾値電圧近傍においてドレイン電流が急激に変化すること）を確立することが重要となる。 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. For the practical use of such a transistor, its manufacturing process (for example, a technique of selectively applying an organic semiconductor layer only to a part that functions as a channel) and 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.
　薄膜トランジスタにおいては、ゲート電極膜と、半導体膜とがゲート絶縁膜を介して重畳して配置される。一般的には、半導体膜がゲート絶縁膜を介してゲート電極膜上に配置される構造（ボトムゲート型構造）が採用されることが多い。そして、ゲート電極膜に印加される電圧に応じて、半導体膜のゲート絶縁膜近傍の領域にキャリアのチャネルが形成されるか否かが決定されることになる。ここで、薄膜トランジスタに含まれる有機半導体膜におけるキャリア伝導は、有機半導体膜との界面におけるゲート絶縁膜の物理的・化学的な特性の影響を強く受ける。 In the thin film transistor, the gate electrode film and the semiconductor film are arranged so as to overlap with each other via the gate insulating film. In general, 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. Here, 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.
　例えば、特許文献１には、ゲート絶縁膜としてＳｉＯ２を用いる場合、その表面に存在する水酸基、酸素及び水がキャリア伝導のトラップサイトとなることが開示されている。このようなゲート絶縁膜の表面を改良する手段として、例えば、非特許文献１には、ゲート絶縁膜界面に自己組織化単分子膜を形成する処理（ＳＡＭ処理）が有効であることが開示されている。また、非特許文献２には、ゲート絶縁膜として高撥水フッ素樹脂（Ｃｙｔｏｐ（登録商標））を用い、且つ、有機半導体膜としてルブレン単結晶を用いた有機薄膜トランジスタが、ヒステリシスフリー、且つ、著しく急峻なスイッチング特性を示すことが開示されている。ただし、このようなゲート絶縁膜の表面は、当該有機半導体膜に対して極めて高い撥液性を有している。そのため、このようなゲート絶縁膜上における有機半導体膜のパターニングは、後述の煩雑なプロセスを経て行われている。 For example, 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. As a means for improving the surface of such a gate insulating film, for example, 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. ing. Further, in Non-Patent Document 2, 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. It is disclosed that it exhibits steep switching characteristics. However, the surface of such a gate insulating film has extremely high liquid repellency with respect to the organic semiconductor film. Therefore, the patterning of the organic semiconductor film on such a gate insulating film is performed through a complicated process described later.
　有機半導体膜をパターニングする技術としては、例えば、親撥パターンを利用する方法及びバンクを利用する方法が知られている。 As a technique for patterning an organic semiconductor film, for example, a method using a repulsion pattern and a method using a bank are known.
　親撥パターンを利用する方法としては、ゲート絶縁膜界面にＳＡＭ処理を施した後に様々な工夫をしてパターニングする方法が知られている。例えば、特許文献１及び非特許文献３においては、ゲート絶縁膜の全面に対してＳＡＭ処理した後にチャネル形成領域となる箇所以外を露光処理により親液化することが開示されている。これにより、当該露光処理が施された箇所では、塗布された有機半導体膜を構成する材料を溶質として含む溶液がはじかれることが抑制される。さらに、当該露光処理が施された箇所に囲まれた箇所においても有機半導体膜がはじかれることなく残存させることが可能である。他方、非特許文献４においては、ゲート絶縁膜の全面に対してＳＡＭ処理した後にチャネル形成領域となる箇所のみを露光処理により親液化することが開示されている。これにより、当該露光処理が施された箇所のみに対して有機半導体膜を構成する材料を溶質として含む溶液を塗布することが可能である。さらに、特許文献２においては、自己組織化単分子膜の密度の変化を利用した親撥パターンを形成し、有機半導体膜を構成する材料を溶質として含む溶液を親液部のみに塗布する方法が示されている。 As a method of using the repellent pattern, a method of patterning by various means after applying SAM treatment to the interface of the gate insulating film is known. For example, 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. On the other hand, 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.
　また、バンクを利用する方法としては、フォトリソグラフィ工程を用いてバンクを形成し、当該バンクによって有機半導体膜を構成する材料を溶質として含む溶液の流動を阻害することで所望の位置に有機半導体膜を製膜する方法が知られている。例えば、非特許文献５においては、工程当該バンクとしてフッ素樹脂を用いることが開示されている。 Further, as a method of using a bank, a bank is formed by using a photolithography process, and the organic semiconductor film is positioned at a desired position by inhibiting the flow of a solution containing a material constituting the organic semiconductor film as a solute. There is a known method of forming a film. For example, Non-Patent Document 5 discloses that a fluororesin is used as the process bank.
特開２００９－６００３２号公報Japanese Unexamined Patent Publication No. 2009-60032 特開２００８－１９２７２４号公報Japanese Unexamined Patent Publication No. 2008-192724
　本発明の一態様は、従来の方法よりも簡便に製造される薄膜トランジスタを含む半導体装置を提供することを目的の一とする。 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.
　本発明者らは、有機半導体膜を構成する材料を溶質として含む溶液の主成分となる溶媒に対する撥液性を有する絶縁膜上への当該有機半導体膜の製膜に先立って、当該溶媒に対する親液性を有する導電膜を所望の形状に製膜することで、当該有機半導体膜を所望の位置、例えば、トランジスタのチャネル形成領域に製膜できることを見出した。 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.
　すなわち、本発明の一態様の半導体装置は、ゲート絶縁膜として機能する絶縁膜の上であり、且つ、有機半導体膜の下の層において、ソース及びドレインとして機能する導電膜が所望の形状を備えること、又は、ソース及びドレインとして機能する導電膜とは別に所望の形状を備える導電膜が設けられていることを要旨とする。また、本発明の一態様の半導体装置の製造方法は、ゲート絶縁膜として機能する絶縁膜の上であり、且つ、有機半導体膜の下の層において、ソース及びドレインとして機能する導電膜を所望の形状に製膜すること、又は、ソース及びドレインとして機能する導電膜とは別に所望の形状を備える導電膜を製膜することを要旨とする。 That is, in the semiconductor device of one aspect of the present invention, 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.
　例えば、第１導電膜と、第１導電膜上の絶縁膜と、絶縁膜上の第２導電膜及び第３導電膜と、絶縁膜、第２導電膜及び第３導電膜上の有機半導体膜とを含み、第２導電膜は、第１方向に沿って延在する部分を含み、第３導電膜は、第２導電膜から見て、第１方向に位置する第１部分と、第２導電膜と第１部分の間の領域から見て、第１方向と直交する第２方向に位置する第２部分及び第２方向の反対方向である第３方向に位置する第３部分と、第２部分から見て、第１方向の反対方向である第４方向に位置する第４部分と、第３部分から見て、第４方向に位置する第５部分とを含み、第１部分、２部分の少なくとも一部及び第３部分の少なくとも一部は、連続して延在し、絶縁膜の表面自由エネルギーは、第２導電膜の表面自由エネルギー及び第３導電膜の表面自由エネルギーよりも小さい、半導体装置は、本発明の一態様である。 For example, the first conductive film, the insulating film on the first conductive film, the second conductive film and the third conductive film on the insulating film, and the organic semiconductor film on the insulating film, the second conductive film and the third conductive film. The second conductive film includes a portion extending along the first direction, and 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.
　また、第１導電膜を製膜する工程と、第１導電膜上に絶縁膜を製膜する工程と、絶縁膜の第１領域及び第２領域に対して紫外線を照射する工程と、記第１領域及び第２領域に第２導電膜及び第３導電膜をそれぞれ製膜する工程と、絶縁膜、第２導電膜及び第３導電膜上に有機半導体膜を製膜する工程とを含み、第１領域は、第１方向に沿って延在し、第２領域は、第１領域から見て、第１方向に位置する第１部分と、第１領域と第１部分の間の領域から見て、第１方向と直交する第２方向に位置する第２部分及び第２方向の反対方向である第３方向に位置する第３部分と、第２部分から見て、第１方向の反対方向である第４方向に位置する第４部分と、第３部分から見て、第４方向に位置する第５部分とを含み、第１部分、第２部分の少なくとも一部及び第３部分の少なくとも一部は、連続して延在し、有機半導体膜を構成する材料を溶質として含む溶液の主成分となる溶媒の前記ゲート絶縁膜に対する接触角は、溶媒の第２導電膜及び第３導電膜のそれぞれに対する接触角よりも大きく、有機半導体膜を製膜する工程は、溶液を第４方向に沿って塗布する工程を含む、半導体装置の製造方法も、本発明の一態様である。 Further, 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 are described. It 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. Seen, 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. Includes a fourth portion located in the fourth direction, which is the direction, and a fifth portion located in the fourth direction when viewed from the third portion, and includes at least a part of the first portion, the second portion, and the third portion. 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.
　本発明の一態様においては、従来の親撥パターンを利用する方法及びバンクを利用する方法といった煩雑な工程を経ずに有機半導体膜を有する薄膜トランジスタを提供することが可能である。 In one aspect of the present invention, it is possible to provide 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.
本発明の一態様の半導体装置の一例を示す上面図。The top view which shows an example of the semiconductor device of one aspect of this invention. 図１Ａに示されるＡ－Ａ’における断面図。FIG. 2 is a cross-sectional view taken along the line AA'shown in FIG. 1A. 図１Ａに示される半導体装置から有機半導体膜７が除去された状態を示す上面図。Top view showing a state in which the organic semiconductor film 7 is removed from the semiconductor device shown in FIG. 1A. 本発明の一態様の半導体装置の一例を示す上面図。The top view which shows an example of the semiconductor device of one aspect of this invention. 図３Ａに示されるＢ－Ｂ’における断面図。FIG. 3A is a cross-sectional view taken along the line BB'shown in FIG. 3A. 図３Ａに示される半導体装置から有機半導体膜２５が除去された状態を示す上面図。Top view showing a state in which the organic semiconductor film 25 is removed from the semiconductor device shown in FIG. 3A. 本発明の一態様の半導体装置の製造方法の一例を示す断面図。The cross-sectional view which shows an example of the manufacturing method of the semiconductor device of one aspect of this invention. 本発明の一態様の半導体装置の製造方法の一例を示す断面図。The cross-sectional view which shows an example of the manufacturing method of the semiconductor device of one aspect of this invention. 本発明の一態様の半導体装置の製造方法の一例を示す断面図。The cross-sectional view which shows an example of the manufacturing method of the semiconductor device of one aspect of this invention. 本発明の一態様の半導体装置の製造方法の一例を示す断面図。The cross-sectional view which shows an example of the manufacturing method of the semiconductor device of one aspect of this invention. ゲート電極膜１５を構成する材料を溶質として含む溶液の塗布方法の一例を示す側面図。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. 有機半導体膜２５を構成する材料を溶質として含む溶液の塗布方法の一例を示す上面図。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. 図７Ａに示されるＣ－Ｃ’における断面図。FIG. 6 is a cross-sectional view taken along the line CC'shown in FIG. 7A. 有機半導体膜２５を構成する材料を溶質として含む溶液の塗布方法の一例を示す上面図。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. 図８Ａに示されるＣ－Ｃ’における断面図。FIG. 6 is a cross-sectional view taken along the line CC'shown in FIG. 8A. 有機半導体膜２５を構成する材料を溶質として含む溶液の塗布方法の一例を示す上面図。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. 図９Ａに示されるＣ－Ｃ’における断面図。FIG. 9 is a cross-sectional view taken along the line CC'shown in FIG. 9A. 有機半導体膜２５を構成する材料を溶質として含む溶液の塗布方法の一例を示す上面図。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. 図１０Ａに示されるＣ－Ｃ’における断面図。FIG. 4 is a cross-sectional view taken along the line CC'shown in FIG. 10A. 有機半導体膜２５を構成する材料を溶質として含む溶液の塗布方法の一例を示す上面図。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. 図１０Ａに示されるＣ－Ｃ’における断面図。FIG. 4 is a cross-sectional view taken along the line CC'shown in FIG. 10A. 半導体装置の変更例を示す断面図。The cross-sectional view which shows the modification example of the semiconductor device. 半導体装置において最初に有機半導体膜が製膜される導電膜の変更例を示す上面図。Top view showing a modification example of a conductive film in which an organic semiconductor film is first formed in a semiconductor device. 半導体装置において最初に有機半導体膜が製膜される導電膜の変更例を示す上面図。Top view showing a modification example of a conductive film in which an organic semiconductor film is first formed in a semiconductor device. 半導体装置において最初に有機半導体膜が製膜される導電例を示す上面図。Top view showing a conductive example in which an organic semiconductor film is first formed in a semiconductor device. 実施例１により得られた半導体装置の偏光顕微鏡写真。A polarizing microscope photograph of the semiconductor device obtained in Example 1. 実施例１により得られた半導体装置に含まれる有機薄膜トランジスタ素子の出力特性を示す図。The figure which shows the output characteristic of the organic thin film transistor element included in the semiconductor device obtained by Example 1. FIG. 実施例１により得られた半導体装置に含まれる有機薄膜トランジスタ素子の伝達特性を示す図。The figure which shows the transmission characteristic of the organic thin film transistor element included in the semiconductor device obtained by Example 1. FIG. 実施例３により得られた半導体装置の偏光顕微鏡写真。A polarizing microscope photograph of the semiconductor device obtained in Example 3. 実施例３により得られた半導体装置に含まれる有機薄膜トランジスタ素子の出力特性を示す図。The figure which shows the output characteristic of the organic thin film transistor element included in the semiconductor apparatus obtained in Example 3. FIG. 実施例３により得られた半導体装置に含まれる有機薄膜トランジスタ素子の伝達特性を示す図。The figure which shows the transmission characteristic of the organic thin film transistor element included in the semiconductor device obtained in Example 3. FIG. 実施例６により得られた半導体装置の偏光顕微鏡写真。A polarizing microscope photograph of the semiconductor device obtained in Example 6. 実施例８により得られた半導体装置の偏光顕微鏡写真。A polarizing microscope photograph of the semiconductor device obtained in Example 8. 実施例１０により得られた半導体膜を示す偏光顕微鏡写真。A polarizing micrograph showing a semiconductor film obtained in Example 10. 実施例１１により得られた半導体装置の偏光顕微鏡写真。A polarizing microscope photograph of the semiconductor device obtained in Example 11. 実施例１３により得られた半導体装置の偏光顕微鏡写真。A polarizing microscope photograph of the semiconductor device obtained in Example 13. 実施例１５により得られた半導体装置の偏光顕微鏡写真。A polarizing microscope photograph of the semiconductor device obtained in Example 15. 実施例１６により得られた半導体装置の偏光顕微鏡写真。A polarizing microscope photograph of the semiconductor device obtained in Example 16. 実施例１７により得られた半導体装置の偏光顕微鏡写真。A polarizing microscope photograph of the semiconductor device obtained in Example 17. 比較例１により得られた半導体装置の偏光顕微鏡写真。A polarizing micrograph of a semiconductor device obtained in Comparative Example 1.
１　半導体装置の一例
（１）構造について
ア　ソース及びドレインとして機能する導電膜が所望の形状を備える場合の一例
　図１Ａ及び１Ｂは、本発明の一態様の半導体装置の一例を示す図である。具体的には、図１Ａは半導体装置の上面図であり、また、図１Ｂは図１Ａの線分Ａ－Ａ’における断面図である。また、図２は、図１Ａに示される半導体装置から有機半導体膜７を除去した状態を示す上面図である。 1 Example of a semiconductor device (1) An example of a case where a conductive film functioning as a source and a drain has a desired shape with respect to a structure 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.
　図１Ａ及び１Ｂに示される半導体装置は、基体１と、基体１上の下地膜２と、下地膜２上の導電膜３と、導電膜３上の絶縁膜４と、絶縁膜４上の導電膜５及び導電膜６と、絶縁膜４、導電膜５及び導電膜６上の有機半導体膜７とを含む。そして、当該半導体装置は、トランジスタとして機能する。具体的には、導電膜３がゲートとして機能し、導電膜５がソース及びドレインの一方として機能し、導電膜６がソース及びドレインの他方として機能する。 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. Then, the semiconductor device functions as a transistor. Specifically, the conductive film 3 functions as a gate, the conductive film 5 functions as one of the source and the drain, and the conductive film 6 functions as the other of the source and the drain.
　導電膜５及び６は、絶縁膜４上にあり、且つ、有機半導体膜７の下にある層において、互いに分離して配置されている。そして、導電膜５は、図１Ａ及び２の紙面上において左から右に向かって延在する部分を含む。また、導電膜６は、図１Ａ及び２の紙面上において導電膜５の右側の末端を囲むように延在する。換言すると、導電膜５は、第１方向に沿って延在し、導電膜６は、導電膜５から見て、第１方向に位置する第１部分６－１と、導電膜５と第１部分６－１の間の領域８－１から見て、第１方向と直交する第２方向に位置する第２部分６－２及び第２方向の反対方向である第３方向に位置する第３部分６－３と、第２部分６－２から見て、第１方向の反対方向である第４方向に位置する第４部分６－４と、第３部分６－３から見て、第４方向に位置する第５部分６－５とを含む。 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. In other words, the conductive film 5 extends along the first direction, and 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.
　また、図１Ａ及び２に示される導電膜６の形状は、「コ」の字状であると表現することもできる。具体的には、導電膜６は、導電膜５が延在する方向、すなわち、上記の第１方向及び第４方向に沿って延在する上方部分及び下方部分と、導電膜５が延在する方向と直交する方向、すなわち、上記の第２方向及び第３方向に沿って延在する中間部分とからなる。そして、典型的には、上方部分の第１方向側の末端と中間部分の第２方向側の末端が連続し、且つ、下方部分の第１方向側の末端と中間部分の第３方向側の末端が連続している。ただし、後述する有機半導体膜６の製膜に支障がない限り、上方部分の第１方向側の末端と中間部分の第２方向側の末端が必ずしも連続せずともよく、これらの末端の間にある程度の空間が存在することもできる。同様に、下方部分の第１方向側の末端と中間部分の第３方向側の末端についても、後述する有機半導体膜の製膜に支障がない限り、これらの末端は必ずしも連続せずともよく、両末端の間にある程度の空間が存在することもできる。なお、当該中間部分は、図１Ａ及び２に示される第１部分６－１を含む。また、当該上方部分は、図１Ａ及び２に示される第２部分６－２及び第４部分６－４を含む。また、当該下方部分は、図１Ａ及び２に示される第３部分６－３及び第５部分６－５を含む。そして、導電膜６は、導電膜５の少なくとも一部が、当該上方部分と当該下方部分の間に位置するように配置されている。 Further, the shape of the conductive film 6 shown in FIGS. 1A and 2 can be expressed as a "U" shape. Specifically, 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. However, as long as there is no problem in forming the organic semiconductor film 6 described later, the end on the first direction side of the upper portion and the end on the second direction side of the intermediate portion do not necessarily have to be continuous, and between these ends. There can be some space. Similarly, with respect to the end on the first direction side of the lower portion and the end on the third direction side of the intermediate portion, these ends do not necessarily have to be continuous as long as the film formation of the organic semiconductor film described later is not hindered. There can also be some space between the ends. 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.
イ　ソース及びドレインとして機能する導電膜とは別に所望の形状を備える導電膜が設けられている場合の一例
　図３Ａ及び３Ｂは、本発明の一態様の半導体装置の他の一例を示す図である。具体的には、図３Ａは半導体装置の上面図であり、また、図３Ｂは図３Ａの線分Ｂ－Ｂ’における断面図である。また、図４は、図３Ａに示される半導体装置から有機半導体膜２５を除去した状態を示す上面図である。 B. Example of a case where a conductive film having a desired shape is provided in addition to the conductive film functioning as a source and a drain. 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.
　図３Ａ及び３Ｂに示される半導体装置は、基体１１と、基体１１上の下地膜１３と、下地膜１３上の導電膜１５と、導電膜１５上の絶縁膜１７と、絶縁膜１７上の導電膜１９、２１及び２３と、絶縁膜１７及び導電膜１９、２１及び２３上の有機半導体膜２５とを含む。そして、当該半導体装置は、トランジスタとして機能する。具体的には、導電膜１５がゲートとして機能し、導電膜１９がソース及びドレインの一方として機能し、導電膜２１がソース及びドレインの他方として機能する。 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.
　導電膜１９、２１及び２３は、絶縁膜１７上にあり、且つ、有機半導体膜２５の下にある層において、互いに分離して配置されている。そして、導電膜１９及び２１は、図３Ａ及び４の紙面上において左から右に向かって略平行に延在する部分を含む。また、導電膜２３は、図３Ａ及び４の紙面上において導電膜１９及び２１の右側の末端を囲むように延在する。換言すると、導電膜１９及び２１は、第１方向に沿って略平行に延在し、導電膜２３は、導電膜１９及び２１から見て、第１方向に位置する第１部分２３－１と、導電膜１９及び２１と第１部分２３－１の間の領域３０－１から見て、第１方向と直交する第２方向に位置する第２部分２３－２及び第２方向の反対方向である第３方向に位置する第３部分２３－３と、第２部分２３－２から見て、第１方向の反対方向である第４方向に位置する第４部分２３－４と、第３部分２３－３から見て、第４方向に位置する第５部分２３－５とを含む。 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. , In the direction opposite to the second portion 23-2 and the second direction located in the second direction orthogonal to the first direction, as viewed from the region 30-1 between the conductive films 19 and 21 and the first portion 23-1. 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, and a third part. Includes a fifth portion 23-5 located in the fourth direction as viewed from 23-3.
　また、図３Ａ及び４に示される導電膜２３の形状は、図１Ａ及び２に示される導電膜６と同様に「コ」の字状であると表現することもできる。 Further, 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.
ウ　半導体装置の構造の特徴について
　図１Ａ及び１Ｂ並びに３Ａ及び３Ｂに示される半導体装置においては、絶縁膜４及び１７として、有機半導体膜７及び２５を構成する材料を溶質として含む溶液の主成分である溶媒に対する撥液性を有する絶縁膜が適用され、また、ソース及びドレインとして機能する導電膜５、６、１９及び２１並びに導電膜２３として、当該溶媒に対する親液性を有する導電膜が適用されている。すなわち、絶縁膜４及び１７の表面自由エネルギーは、導電膜５、６、１９、２１及び２３の表面自由エネルギーよりも小さい。そのため、当該溶媒の絶縁膜４及び１７に対する接触角は、当該溶媒の導電膜５、６、１９、２１及び２３のそれぞれに対する接触角よりも大きくなる。 C. Structural features of semiconductor devices In the semiconductor devices shown in FIGS. 1A and 1B and 3A and 3B, 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.
　なお、導電膜６及び２３の形状は、図１Ａ、２、３Ａ及び４に示される形状に限定されない。ただし、薄膜トランジスタのチャネル形成領域となる導電膜５と導電膜６の間の領域（図１Ａ及び２参照）又は導電膜１９と導電膜２１の間の領域（図３Ａ及び４参照）における絶縁膜４又は１７上に有機半導体膜７又は２５を製膜するために以下のような形状に製膜される必要がある。 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.
　まず、後述する有機半導体膜７又は２５の製膜工程において、有機半導体膜７又は２５を構成する材料を溶質として含む溶液は、図１Ａ、２、３Ａ及び４の紙面上において、右から左に向かって、すなわち、上記の第４方向に沿って塗布される。上述のとおり、絶縁膜４及び１７は当該溶液の主成分である溶媒に対する撥液性を有し、また、導電膜６及び２３は当該溶媒に対する親液性を有するため、当該溶液の塗布は、導電膜６及び２３と当該溶液の接触を契機として開始されることになる。なお、本明細書において、塗布が開始されるとは、塗装される溶液がブレード及びローラ等の塗布部材から分離・独立して被塗装物上に残存し始めることを言う。そして、当該溶液の塗布は、薄膜トランジスタのチャネル形成領域となる導電膜５と導電膜６の間の領域（図１Ａ及び２参照）又は導電膜１９と導電膜２１の間の領域（図３Ａ及び４参照）における絶縁膜４又は１７と、当該溶液とが接触する前に開始されなければならない。そのため、導電膜６は、導電膜５から見て、上記の第１方向に存在する部分（例えば、第１部分６－１）を含むような形状に製膜される必要がある。同様に、導電膜２３は、導電膜１９及び導電膜２１から見て、上記の第１方向に存在する部分（例えば、第１部分２３－１）を含むような形状に製膜される必要がある。 First, in the film forming process of the organic semiconductor film 7 or 25 described later, 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. As described above, the insulating films 4 and 17 have liquid repellency to the solvent which is the main component of the solution, and 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. In the present specification, 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. Then, 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.
　また、後述する有機半導体膜７及び２５の製膜工程において、溶液に溶質として含まれる有機半導体膜７及び２５を構成する材料が、その塗布方向における導電膜５と、導電膜６との間の領域（図１Ａ及び２に示される領域８－１）又はその塗布方向における導電膜１９及び２１と、導電膜２３との間の領域（図３Ａ及び４に示される領域３０－１）に析出して残存する必要がある。換言すると、当該製造工程において、当該溶液が、領域６－１及び３０－１から当該溶液が塗布される方向と直交する方向、すなわち、上記の第２方向及び第３方向にはじかれることを防止する必要がある。そのため、導電膜６は、領域８－１から見て、上記の第２方向及び第３方向に存在する部分（例えば、第２部分６－２及び第３部分６－３）を含み、且つ、該部分の少なくとも一部が上記の第１方向に存在する部分（例えば、第１部分６－１）から連続して延在するような形状に製膜される必要がある。同様に、導電膜２３は、領域３０－１から見て、上記の第２方向及び第３方向に存在する部分（例えば、第２部分２３－２及び第３部分２３－３）を含み、且つ、該部分の少なくとも一部が上記の第１方向に存在する部分（例えば、第１部分２３－１）から連続して延在するような形状に製膜される必要がある。 Further, in the film forming process of the organic semiconductor films 7 and 25 described later, 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. Therefore, 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). Similarly, 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).
　同様に、後述する有機半導体膜７及び２５の製膜工程において、溶液に溶質として含まれる有機半導体膜７及び２５を構成する材料が、その塗布方向と直交する方向における導電膜５と導電膜６の間の領域（図１Ａ及び２に示される領域８－２及び８－３）に、又は、その塗布方向と直交する方向における導電膜１９と導電膜２３の間の領域（図３Ａ及び４に示される領域３０－２）及び導電膜２１と導電膜２３の間の領域（図３Ａ及び４に示される領域３０－３）にある程度残存する必要がある。換言すると、当該製膜工程において、当該溶液が、領域６－１、６－２、３０－１及び領域３０－２から当該溶液が塗布される方向、すなわち、上記の第４方向にはじかれることを防止する必要がある。そのため、導電膜６は、上記の第２方向及び第３方向において、導電膜５と重畳する部分（例えば、第４部分６－４及び第５部分６－５）を含むような形状に製膜される必要がある。同様に、導電膜２３は、上記の第２方向及び第３方向において、導電膜１９及び２１と重畳する部分（例えば、第４部分２３－４及び第５部分２３－５）を含むような形状に製膜される必要がある。 Similarly, in the film forming process of the organic semiconductor films 7 and 25 described later, 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. In the region between (regions 8-2 and 8-3 shown in FIGS. 1A and 2), or in the region between the conductive film 19 and the conductive film 23 in the direction orthogonal to the coating direction thereof (in FIGS. 3A and 4). It is necessary to remain to some extent in the indicated region 30-2) and the region between the conductive film 21 and the conductive film 23 (region 30-3 shown in FIGS. 3A and 4). In other words, in the film forming process, the solution is repelled from the regions 6-1 and 6-2, 30-1 and the region 30-2 in the direction in which the solution is applied, that is, in the fourth direction described above. Need to be prevented. Therefore, 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. Similarly, 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.
　また、図１Ａ及び１Ｂ並びに２においては図示されていないが、導電膜３、５及び６は、他の回路素子（トランジスタ、信号線及び電源線等）と電気的に接続されている。同様に、図３Ａ及び３Ｂ並びに４においては図示されていないが、導電膜１５、１９及び２１は、他の回路素子と電気的に接続されている。他方、図３Ａ及び３Ｂ並びに４に示される導電膜２３は、他の回路素子に接続されていない、すなわち、電気的に孤立している。 Although not shown in FIGS. 1A, 1B, and 2, the conductive films 3, 5 and 6 are electrically connected to other circuit elements (transistors, signal lines, power supply lines, etc.). Similarly, although not shown in FIGS. 3A, 3B and 4, the conductive films 15, 19 and 21 are electrically connected to other circuit elements. On the other hand, the conductive film 23 shown in FIGS. 3A, 3B and 4 is not connected to other circuit elements, that is, is electrically isolated.
（２）材料について
ア　基体１及び１１
　基体１及び１１として、ポリエチレンナフタレート（ＰＥＮ）、ポリエチレンテレフタレート（ＰＥＴ）若しくはポリプロピレンのような耐熱性の低いプラスチック基板又はポリカーボネートのような耐熱性の高いプラスチック基板、シリコン基板、ガラス基板等を適用することできる。基体１及び１１としてプラスチック基板のようなフレキシブルな基板を適用する場合、半導体装置全体をフレキシブルにすることができるため好ましい。また、基体１及び１１としてフッ素樹脂を含浸させたパルプ基板を適用してもよい。 (2) Materials A. 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.
イ　下地膜２及び１３及び絶縁膜４及び１７
　下地膜２及び１３並びに絶縁膜４及び１７は、フッ素系樹脂を含んでいてもよい。また、下地膜２及び１３並びに絶縁膜４及び１７は、フッ素系樹脂からなっていてもよい。なお、下地膜２及び１３並びに絶縁膜４及び１７の表面は、凹凸のない滑らかな表面であることが好ましい。また、本発明の一態様における下地膜２及び１３及び絶縁膜４及び１７は、紫外線を照射することにより光化学反応ラジカルを生じる必要がある（詳細は後述する）。そのため、下地膜２及び１３並びに絶縁膜４及び１７として反応性ラジカルを生じるフッ素系樹脂等のポリマー絶縁材料を適用することが好ましい。 B. Undercoat films 2 and 13 and insulating films 4 and 17
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.
　当該フッ素系樹脂の一例としては、ポリクロロトリフルオロエチレン、ポリビニルフルオライド、エチレン－クロロトリフルオロエチレンコポリマー、ポリビニリデンフルオライド、パーフルオロエチレンプロペンコポリマー、エチレン－ テトラフルオロエチレンコポリマー、ポリテトラフルオロエチレン、パーフルオロアルコキシアルカンやパーフルオロアルキルエーテル環構造を有するフッ素系樹脂等が挙げられる。 Examples of the fluororesin include polychlorotrifluoroethylene, polyvinylfluoride, ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride, perfluoroethylene propene copolymer, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, and the like. Examples thereof include perfluoroalkoxyalkane and a fluororesin having a perfluoroalkyl ether ring structure.
　さらに、下地膜２及び１３並びに絶縁膜４及び１７として、パーフルオロ樹脂、特にパーフルオロアルキルエーテル環構造を有するフッ素系樹脂を用いることがより好ましい。これにより、特性に優れるトランジスタが得られるからである。例えば、パーフルオロ（３ブテニルビニルエーテル）重合体（ＡＧＣ社製ＣＹＴＯＰ（登録商標））又はパーフルオロジメチルジオキソール－テトラフルオロエチレン共重合体（テフロン（登録商標）ＡＦ）等は、下地膜２及び１３並びに絶縁膜４及び１７に適用される材料として特に好ましい。 Further, it is more preferable to use a perfluoro resin, particularly a fluororesin having a perfluoroalkyl ether ring structure, as the undercoat films 2 and 13 and the insulating films 4 and 17. This is because a transistor having excellent characteristics can be obtained. For example, a perfluoro (3 butenyl vinyl ether) polymer (CYTOP (registered trademark) manufactured by AGC) or a perfluorodimethyldioxol-tetrafluoroethylene copolymer (Teflon (registered trademark) AF) may be used as the base film 2. And 13 and the materials applied to the insulating films 4 and 17 are particularly preferable.
ウ　導電膜３、５、６、１５、１９、２１及び２３
　導電膜３、５、６、１５、１９、２１及び２３は、金属若しくはそれを含む合金、導電性有機物又は金属ナノ粒子が分散されている有機物を含んでいてもよい。また、導電膜３、５、６、１５、１９、２１及び２３は、金属若しくはそれを含む合金、導電性有機物又は金属ナノ粒子が分散されている有機物からなっていてもよい。さらに、図１Ａ及び１Ｂ並びに２に示される導電膜５及び６は、同一材料からなっていてもよい。また、図３Ａ及び３Ｂ並びに４に示される導電膜１９、２１及び２３は、同一材料からなっていてもよい。この場合、導電膜５及び６又は導電膜１９、２１及び２３を同時に製膜することができるため好ましい。 C. Conductive films 3, 5, 6, 15, 19, 21 and 23
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.
　導電膜３、５、６、１５、１９、２１及び２３に含まれる金属又はそれを含む合金の一例としては、白金、金、銀、アルミニウム、クロム、タングステン、銅、鉄、鉛、チタン、インジウム等の金属及びそれらを含む合金（ＩｎО２、ＺｎＯ２、及び酸化インジウムスズ（ＩＴＯ）等）等が挙げられる。 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 (InО 2 , ZnO 2 , and indium tin oxide (ITO), etc.) and the like.
　導電膜３、５、６、１５、１９、２１及び２３に含まれる導電性有機物としては、ポリチオフェン、ポリアセチレン、ポリパラフェニレンビニレン等の導電性高分子化合物、カーボンナノチューブ及びグラフェン等が挙げられる。 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.
　導電膜３、５、６、１５、１９、２１及び２３に含まれる金属ナノ粒子が分散されている有機物の一例としては、テトラクロロメタン、ベンゼン、ジクロロベンゼン、ジクロロメタン、トルエン、オクタン、テトラリン、メシチレン、ブタノール、メタノール等が挙げられる。 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.
　当該有機物に分散されている金属ナノ粒子の一例としては、金、銀又は銅を主成分として他の金属元素を含有する金属ナノ粒子が挙げられる。なお、当該金属ナノ粒子は、ナノサイズと一般に呼ばれるサイズ（１μｍ未満）であり、平均粒径が１０ｎｍ以上で１００ｎｍ以下が好ましく、より好ましくは３０ｎｍ以下である。また、金属ナノ粒子が金又は銀を含む場合、得られる電極膜の導電率が高くなるため好ましい。 Examples of 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 μm), 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.
　また、当該金属ナノ粒子の割合は、材料の全質量に対して、重量％で３０％以上６０％以下であることが好ましい。これにより、導電膜３、５、６、１５、１９、２１及び２３の厚みを好適な範囲（１５～１００ｎｍの範囲、特に３０～９０ｎｍの範囲）とした場合に、これらを所望のパターンに製膜することが容易になる。 Further, 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. As a result, when the thicknesses of the conductive films 3, 5, 6, 15, 19, 21 and 23 are set in a suitable range (range of 15 to 100 nm, particularly in the range of 30 to 90 nm), these can be produced in a desired pattern. It becomes easy to film.
　また、金属ナノ粒子は、アルキルアミン、アルキルジアミン、若しくはその他の構造のアミンを含む有機分子層で被覆されていてもよい。この被覆部分は、多数のアルキルアミン分子がアミノ基の配位結合により金属ナノ粒子に接合し、そのアルキル基部分が金属ナノ粒子表面で凝集することにより形成されているものと考えられる。このため、被覆部分の重量割合は、主に使用するアルキルアミンの分子量を調整することにより調整することができる。 Further, 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.
　金属ナノ粒子を被覆するアルキルアミン、アルキルジアミン、若しくはその他の構造のアミンを含む有機分子層の一例としては、次のものが挙げられる。 Examples of organic molecular layers containing alkylamines, alkyldiamines, or amines having other structures that coat metal nanoparticles include the following.
　まず、中短鎖アルキルアミンは、特に、その構造に制限がないが、一級アミノ基であるＲＮＨ２（Ｒは炭化水素鎖）または二級アミノ基であるＲ１Ｒ２ＮＨ（Ｒ１、Ｒ２は炭化水素鎖で同じであっても異なっていてもよい）であることが望ましい。また、中短鎖アルキルアミンとしては、錯化合物の熱分解温度を考慮すれば１００℃以上の沸点であること、また、被覆された金属ナノ粒子の低温焼結性を考慮すれば、２５０℃以下の沸点であることが考慮される。例えば、２－エトキシエチルアミン、ジプロピルアミン、ジブチルアミン、ヘキシルアミン、シクロヘキシルアミン、ヘプチルアミン、３－ブトキシプロピルアミン、オクチルアミン、ノニルアミン、デシルアミン、３－アミノプロピルトリエトキシシラン、ドデシルアミン等が挙げられるが、これらに限定されるものではない。 First, 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. For example, 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.
　長鎖・中鎖のアルキルアミンとしては、例えば、ジプロピルアミン、ジブチルアミン、ヘキシルアミン、シクロヘキシルアミン、ヘプチルアミン、３－ブトキシプロピルアミン、オクチルアミン、ノニルアミン、デシルアミン、３－アミノプロピルトリエトキシシラン、ドデシルアミン、ヘキサデシルアミン、オレイルアミン、オクタデシルアミン等のアルキルアミンである。なお、炭素数が６以上の長鎖・中鎖のアルキルアミンであれば、適宜、目的に応じて使用することができる。 Examples of long-chain and medium-chain alkylamines 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.
　短鎖のアルキルアミンとしては、例えば、アミルアミン、２－エトキシエチルアミン、４－メトキシブチルアミン、ジイソプロピルアミン、ブチルアミン、ジエチルアミン、プ
ロピルアミン、イソプロピルアミン、エチルアミン、ジメチルアミン等が挙げられる。 Examples of the short-chain alkylamine include amylamine, 2-ethoxyethylamine, 4-methoxybutylamine, diisopropylamine, butylamine, diethylamine, propylamine, isopropylamine, ethylamine, dimethylamine and the like.
　また、中短鎖アルキルジアミンは、特に、その構造に制限がないが、少なくとも１つのアミノ基が一級アミノ基であるＲＮＨ２（Ｒは炭化水素鎖）または二級アミノ基であるＲ１Ｒ２ＮＨ（Ｒ１、Ｒ２は炭化水素鎖で同じであっても異なっていてもよい）であることが望ましい。中短鎖アルキルジアミンとしては、錯化合物の熱分解温度を考慮すれば１００℃以上の沸点であること、また、被覆された金属ナノ粒子の低温焼結性を考慮すれば、２５０℃以下の沸点であることが考慮される。例えば、エチレンジアミン、Ｎ，Ｎ－ジメチルエチレンジアミン、Ｎ，Ｎ’－ジメチルエチレンジアミン、Ｎ，Ｎ－ジエチルエチレンジアミン、Ｎ，Ｎ’－ジエチルエチレンジアミン、１，３－プロパンジアミン、２，２－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジメチル－１，３－ジアミノプロパン、Ｎ，Ｎ’－ジメチル－１，３－ジアミノプロパン、Ｎ，Ｎ－ジエチル－１，３－ジアミノプロパン、１，４－ジアミノブタン、１，５－ジアミノ－２－メチルペンタン、１，６－ジアミノヘキサン、Ｎ，Ｎ’－ジメチル－１，６－ジアミノヘキサン、１，７－ジアミノヘプタン、１，８－ジアミノオクタン等が挙げられるが、これらに限定されるものではない。 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. For example, ethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N-diethylethylenediamine, N, N'-diethylethylenediamine, 1,3-propanediamine, 2,2-dimethyl-1,3. -Propane diamine, N, N-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopropane, 1,4-diaminobutane , 1,5-Diamino-2-methylpentane, 1,6-diaminohexane, N, N'-dimethyl-1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane and the like. However, it is not limited to these.
エ　有機半導体膜７及び２５
　有機半導体膜７及び２５は、高分子有機半導体材料及び低分子有機半導体材料の一方又は双方を含んでもよい。なお、本明細書において、高分子とは、分子量が１００００を超える分子を意味し、また、低分子とは、分子量が１００００を以下の分子を意味する。有機半導体膜７及び２５を構成する有機半導体材料としては、低分子有機半導体材料であることが好ましい。さらに、低分子有機半導体材料の分子量が１５００以下であることが好ましく、８００以下であることがより好ましい。なお、当該有機半導体材料の分子骨格は、半導体性能を有するものであれば特に限定されない。 D. Organic semiconductor films 7 and 25
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. In the present specification, the polymer means a molecule having a molecular weight of more than 10,000, and 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. Further, 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.
　有機半導体膜７及び２５を構成する低分子有機半導体材料としては、縮合多環芳香族化合物が好ましく、アセン骨格またはヘテロアセン骨格を有する縮合多環芳香族化合物がより好ましく、チエノアセン骨格を有する縮合多環芳香族化合物が特に好ましく、下式（２）又は（３）で表される化合物が最も好ましい。また、当該有機半導体材料は、有機半導体膜７及び２５を製膜する際に有機溶剤に溶解されることになるため、溶剤溶解性があることが好ましい。例えば、当該有機半導体材料が溶解性の確保のためにアルキル基を有していることが好ましい。なお、チエノアセン骨格とは、下式（１）に示すチオフェン環構造を分子構造内に少なくとも一つ以上、縮環部位として含む化合物を指す。 As the low molecular weight organic semiconductor material constituting the organic semiconductor films 7 and 25, 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. Further, since 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. For example, it is preferable that 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.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（２）中、Ｒ１はアルキル基を表す。また、Ｒ２は、アルキル基を有していてもよい芳香族炭化水素基又はアルキル基を有していてもよい複素環基を表す。また、式（３）中、Ｒ３及びＲ５が水素原子である場合、Ｒ４及びＲ６の一方がアルキル基、他方がアルキル基を有していてもよい芳香族炭化水素基又はアルキル基を有していてもよい複素環基を表す。また、式（３）中、Ｒ３乃至Ｒ６のいずれか三つが水素原子である場合、残りの一つがアルキル基を表す。 In formula (2), R1 represents an alkyl group. Further, R2 represents an aromatic hydrocarbon group which may have an alkyl group or a heterocyclic group which may have an alkyl group. Further, in the formula (3), when 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. Represents a optionally heterocyclic group. Further, in the formula (3), when any three of R3 to R6 are hydrogen atoms, the remaining one represents an alkyl group.
　これらのアルキル基は、直鎖、分岐鎖及び環状のいずれにも限定されない。例えば、これらのアルキル基の一例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－オクチル基、ｎ－デシル基、ｎ－ドデシル基、２－エチルヘキシル基等が挙げられる。なお、これらのアルキル基としては、直鎖アルキル基が好ましく、炭素数４乃至１４の直鎖アルキル基がより好ましく、炭素数６乃至１２の直鎖アルキル基が更に好ましく、炭素数８乃至１２の直鎖アルキル基が最も好ましい。 These alkyl groups are not limited to straight chain, branched chain and cyclic. For example, 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. As these alkyl groups, 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.
　アルキル基を有していてもよい芳香族炭化水素基は、芳香族炭化水素上の水素原子の一つがアルキル基に置換された官能基を意味し、その具体例としては、フェニル基、ナフチル基、アンスリル基等が挙げられる。なお、芳香族炭化水素基としては、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。 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. As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
　アルキル基を有していてもよい複素環基は、芳香族炭化水素基を複素環基に置き換えた同様の様態を表す。複素環基の例としては、ピリジル基、ピラジル基、ピリミジル基、イミダゾリル基、チエニル基、ベンゾチエニル基などが挙げられる。なお、好ましい複素環基としては、チエニル基又はベンゾチエニル基が挙げられる。 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. Examples of 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. In addition, a preferable heterocyclic group includes a thienyl group or a benzothienyl group.
　有機半導体膜７及び２５を構成する高分子有機半導体材料としては、例えば、ポリチオフェン、ポリフェニレンビニレン、ポリフルオレン、ポリアセチレン、ポリピロールなどのほか、ベンゾジチオフェンやチエノチオフェンなどの電子密度の高いモノマーとベンゾチアジアゾール、ベンゾビスチアジアゾール、ジケトピロロピロールなどの電子密度の低いモノマーを共重合することにより得られるドナー・アクセプター型ポリマーなどを挙げることができる。 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.
　半導体装置の特性を改善する、又は、他の特性を付与する目的で二つ以上の材料が混合されて有機半導体膜７及び２５を構成する有機半導体材料として使用されてもよい。混合される有機半導体材料は、高分子有機半導体材料および低分子有機半導体材料のいずれであってもよい。一般的に、薄膜トランジスタの特性は、半導体膜の結晶性が高いほど良好になる。例えば、Ａｄｖ．Ｍａｔｅｒ．２０１８．３０．１７０７２５６には、二種類の低分子有機半導体材料を混合して使用することで、結晶性の高い有機半導体膜が得られることが記載されている。そのため、二つ以上の材料が混合された有機半導体材料を用いて有機半導体膜７及び２５を製膜する場合、当該二つの材料の双方が低分子有機半導体材料であることが好ましい。さらに、当該二つの材料が同一の分子構造を有し、且つ、アルキル基の長さの異なる低分子有機半導体であることがより好ましい。 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. Generally, the higher the crystallinity of the semiconductor film, the better the characteristics of the thin film transistor. For example, 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.
　また、これらの材料は、溶媒となる有機物に分散されていてもよい。すなわち、有機半導体膜７及び２５は、これらの材料が分散される有機物からなっていてもよい。さらに、有機半導体膜７及び２５は、添加物を含んでいてもよい。 Further, 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.
　有機半導体膜７及び２５に含まれる添加物は、半導体装置の機能を阻害しないものであれば特に制限はない。例えば、当該添加物の一例として、絶縁性材料、レオロジー制御のための界面活性剤又は増粘剤、キャリア注入又はキャリア量を調整するためのドーパントなどが挙げられる。 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. For example, 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.
　これらの材料の溶媒となる有機物としては、これらの材料を溶解・分散しうるものであれば特に限定なく用いることができるが、保存安定性を考慮した場合、材料を溶解しうる溶媒であることが望ましい。当該有機物の一例としては、クロロホルム、クロロベンゼン、ジクロロベンゼン等のハロゲン系溶媒、ベンゼン、トルエン、キシレン、メシチレン、テトラリン、シクロヘキシルベンゼン等の芳香族炭化水素系溶媒、テトラヒドロフラン、アニソール、フェネトール等のエーテル類、ジメチルホルムアミド、ジメチルアセトアミド等のアミド類、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノン等のケトン類、安息香酸メチル、安息香酸エチル等のエステル類、及び、シクロヘキサン、デカリン等の炭化水素類等が挙げられる。 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. Examples of 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.
２　半導体装置の製造方法の一例
　図５Ａ～５Ｄは、図１Ａ及び１Ｂ並びに２に示される半導体装置の製造方法の一例を示す図であり、具体的には、基体１への下地膜２の製膜（図５Ａ）から導電膜５及び６の製膜（図５Ｄ）までを製膜される順に示す図である。なお、図５Ａ～５Ｄにおいては図１Ａ及び１Ｂ並びに２に示される半導体装置の製造方法の一例を示しているものの、同様の製造方法によって図３Ａ及び３Ｂ並びに４に示される半導体装置を製造することも可能である。 2 Example of Manufacturing Method of Semiconductor Device 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. Although 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.
　まず、下地膜２を構成する材料を溶質として含む溶液を基体１上に塗布する。当該溶液の塗布方法としては、スピンコート法、ディップコート法、スプレーコート法、液滴吐出法及びダイコート法等を適用することができる。下地膜２は平板状の基体１の上面全体に塗布される場合、スピンコーティングを適用することが好ましい。そして、塗布された溶液には、２００℃以下の温度における熱処理が施されてもよいし、自然乾燥されてもよい。以上によって、基体１への下地膜２の製膜が完了する（図５Ａ参照）。 First, a solution containing the material constituting the base film 2 as a solute is applied onto the substrate 1. As a method for applying the solution, 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. When the base film 2 is applied to the entire upper surface of the flat plate-shaped substrate 1, it is preferable to apply spin coating. Then, 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).
　次いで、後に導電膜３が製膜される領域（第１パターン領域）の下地膜２に選択的に紫外線を照射する。紫外線の照射方法としては、第１パターン領域以外をフォトマスクで覆った状態で下地膜２の全面に紫外線を照射する方法及び第１パターン領域のみに紫外線レーザーを照射する方法等を適用することができる。 Next, the base film 2 in the region where the conductive film 3 is later formed (first pattern region) is selectively irradiated with ultraviolet rays. As 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.
　これにより、第１パターン領域における下地膜２の表面は、光化学反応により反応性表面となる。なお、本明細書において、反応性表面とは、紫外線照射にともなうパーフルオロ樹脂等の絶縁膜の光化学反応によって絶縁膜表面にラジカル基を生じ、金属ナノ粒子が分散されている有機物が付着・凝集しやすい状態になっている表面をいう。また、当該金属ナノ粒子がアルキルアミン、アルキルジアミン又はその他の構造のアミンを含む有機分子層で被覆されている場合、当該ラジカル基が当該有機分子層の離脱を促進し、金属ナノ粒子同士の付着・凝集（融着・凝集）が促進される。なお、本明細書において、付着・凝集、又は、融着・凝集とは、金属ナノ粒子が、被製膜物に、付着（融着）しながら凝集していく状態を意味する。 As a result, the surface of the base film 2 in the first pattern region becomes a reactive surface by a photochemical reaction. In the present specification, 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. When the metal nanoparticles are coated with an organic molecular layer containing an alkylamine, an alkyldiamine or an amine having another structure, the radical group promotes the detachment of the organic molecular layer and the metal nanoparticles adhere to each other.・ Aggregation (fusion / aggregation) is promoted. In addition, in this specification, adhesion / agglutination or fusion / aggregation means a state in which metal nanoparticles are adhered (fused) to a film to be formed and aggregated.
　下地膜２に照射される紫外線は、下地膜２における炭素（Ｃ）とフッ素（Ｆ）の結合を乖離させること等を目的として照射されるものである。そして、炭素（Ｃ）とフッ素（Ｆ）の結合エネルギーは、４９０ｋＪ／ｍｏｌ程度である。そのため、当該紫外線の波長が２４４ｎｍ以下であれば炭素（Ｃ）とフッ素（Ｆ）の結合を乖離させることができると考えられる。例えば、当該紫外線の波長としては、１０ｎｍ～２４４ｎｍであればよく、１０ｎｍ～２００ｎｍであることが好ましく、１００ｎｍ～２００ｎｍであることがより好ましい。 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. For example, 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.
　次いで、導電膜３を構成する材料を溶質として含む溶液を下地膜２上に塗布する。当該溶液の塗布方法としては、ブレード及びローラ等の塗布部材を用いる方法を適用することができる。例えば、当該溶液を下地膜２上に滴下するとともに、下地膜２に近接するブレードの掃引又はローラの回転によって当該溶液を下地膜２の第１パターン領域に塗布する方法等を適用することができる。例えば、図６に示されるように、下地膜２上に溶液１５０を滴下するとともに、下地膜２に近接するブレード２００を紙面上の右から左に掃引することによって溶液１５０を下地膜１３の第１パターン領域に塗布すればよい。なお、ブレード２００を掃引する方向は、どのような方向であってもよい。 Next, a solution containing the material constituting the conductive film 3 as a solute is applied onto the undercoat film 2. As a method of applying the solution, a method using an application member such as a blade and a roller can be applied. For example, 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. .. For example, as shown in FIG. 6, 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.
　これにより、第１パターン領域のみに導電膜３を構成する材料を溶質として含む溶液が塗布される。そして、塗布された溶液には、２００℃以下の温度における熱処理が施されてもよいし、自然乾燥されてもよい。以上によって、導電膜３の製膜が完了する（図５Ｂ参照）。なお、下地膜２上への導電膜３の製膜については、特開２０１４－１９５７９４号公報の開示内容を参照してもよい。 As a result, 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.
　次いで、絶縁膜４を構成する材料を溶質として含む溶液を下地膜２及び導電膜３上に塗布する。当該溶液の塗布方法としては、下地膜２を構成する材料を溶質として含む溶液の塗布方法と同様の方法を採用することができるため、上述の説明を援用する。そして、塗布された溶液には、２００℃以下の温度における熱処理が施されてもよいし、自然乾燥されてもよい。以上によって、絶縁膜４の製膜が完了する（図５Ｃ参照）。 Next, 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. As 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. 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 insulating film 4 is completed (see FIG. 5C).
　次いで、後に導電膜５及び６が製膜される領域（第２パターン領域）の絶縁膜４に選択的に紫外線を照射する。紫外線の照射方法としては、下地膜２に対する紫外線の照射方法と同様の方法を採用することができるため、上述の説明を援用する。 Next, the insulating film 4 in the region where the conductive films 5 and 6 are formed (second pattern region) is selectively irradiated with ultraviolet rays. As 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.
　次いで、導電膜５及び６を構成する材料を溶質として含む溶液を絶縁膜４上に塗布する。当該溶液の塗布方法としては、導電膜３を構成する材料を溶質として含む溶液の塗布方法と同様の方法を採用することができるため、上述の説明を援用する。 Next, a solution containing the materials constituting the conductive films 5 and 6 as a solute is applied onto the insulating film 4. As 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.
　これにより、第２パターン領域のみに導電膜５及び６を構成する材料を溶質として含む溶液が塗布される。そして、塗布された溶液には、２００℃以下の温度における熱処理が施されてもよいし、自然乾燥されてもよい。さらに、導電膜５及び６に対して表面処理を施してもよい。当該表面処理の一例としては、水素原子の少なくとも一つがフッ素原子に置換されたベンゼンチオールを用いる表面処理が挙げられる。これにより、後に製膜される有機半導体膜７と、ソース及びドレインとして機能する導電膜５及び６との間の仕事関数の変化が緩和され、キャリア注入効率が改善される、また、当該表面処理によって、有機半導体膜７を構成する材料を溶質として含む溶液の主成分となる溶媒に対する導電膜５及び６の表面の親液性が改善される。以上によって、導電膜５及び６の製膜が完了する（図５Ｄ参照）。なお、絶縁膜４上への導電膜５及び６の製膜については、特開２０１４－１９５７９４号公報の開示内容を参照してもよい。 As a result, 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. As a result, the change in the work function between the organic semiconductor film 7 to be formed later and the conductive films 5 and 6 functioning as sources and drains is alleviated, the carrier injection efficiency is improved, and the surface treatment is improved. As a result, 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. With the above, the film formation of the conductive films 5 and 6 is completed (see FIG. 5D). Regarding the film formation of the conductive films 5 and 6 on the insulating film 4, the disclosure contents of JP-A-2014-195794 may be referred to.
　次いで、有機半導体膜７を構成する材料を溶質として含む溶液を導電膜５及び６並びに絶縁膜４上に塗布する。当該溶液の塗布方法としては、導電膜３、５及び６を構成する材料を溶質として含む溶液の塗布方法と同様の方法を採用することができる。ただし、有機半導体膜７を構成する材料を溶質として含む溶液の塗布は、特定の方向に沿って行われる。 Next, 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. As 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. However, the application of the solution containing the material constituting the organic semiconductor film 7 as a solute is performed along a specific direction.
　有機半導体膜７を構成する材料を溶質として含む溶液の塗布方法の一例について、図７Ａ及び７Ｂ～１１Ａ及び１１Ｂを参照して詳細に説明する。なお、図７Ａ～１１Ａは当該溶液を塗布する際の変化を示す上面図であり、図７Ｂ～１１Ｂは図７Ａ～１１Ａに示されるＣ－Ｃ’における断面図である。 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, and FIGS. 7B to 11B are cross-sectional views taken along the line CC'shown in FIGS. 7A to 11A.
　まず、導電膜６から見て、導電膜５が位置する側とは逆側の方向に位置する絶縁膜４上に有機半導体膜７を構成する材料を溶質として含む溶液２５０を滴下する。そして、図７Ａ及び７Ｂに示されるように、ブレード３００を溶液２５０と接触させるとともに絶縁膜４等と接触しない位置に配置する。なお、ブレード３００は、溶液２５０に対する撥液性を有することが好ましい。例えば、ブレード３００は、溶液２５０に対する撥液性を有するように表面が撥液加工されていることが好ましい。なお、ブレード３００に対する撥液加工の一例としては、絶縁膜４の材料として好適な材料であるパーフルオロ（３ブテニルビニルエーテル）重合体（ＡＧＣ社製ＣＹＴＯＰ（登録商標））又はパーフルオロジメチルジオキソール－テトラフルオロエチレン共重合体（テフロン（登録商標）ＡＦ）等を用いた加工等が挙げられる。そして、図７Ａに示される矢印の方向、すなわち、紙面上の右から左に向かってブレード３００を掃引する。換言すると、ブレード３００は、上記の第４方向に沿って掃引される。 First, 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. For example, it is preferable that the surface of the blade 300 is liquid-repellent so as to have liquid-repellent property against the solution 250. As an example of the liquid-repellent treatment on the blade 300, 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. Then, 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.
　ブレード３００の移動に伴って溶液２５０も導電膜６側に移動すると、図８Ａ及び８Ｂに示されるように溶液２５０が導電膜６上に位置する。ここで、導電膜６は、溶液２５０の主成分となる溶媒に対する親液性を有するため、溶液２５０の後端（図８Ａ及び８Ｂの紙面上の右側の末端）がブレード３００の移動に追従せずに引き延ばされる。また、溶液２５０の後端においては、乾燥（溶媒の揮発）が促進される。その結果、溶液２５０の溶質である有機半導体材料が析出することで、導電膜６上への有機半導体膜７の製膜が開始される。 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. Here, since the conductive film 6 has positivity with respect to the solvent that is the main component of the solution 250, 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.
　図９Ａ及び９Ｂに示されるようにブレード３００が導電膜５と導電膜６の間の領域上にさらに移動すると、溶液２５０の後方部分（図９Ａ及び９Ｂの紙面上の右側の部分）が、既に製膜された有機半導体膜７によって引き延ばされる。また、当該後方部分の後方及び左右に親液性を有する導電膜６が存在することによって、当該後方部分は、導電膜６上に製膜された有機半導体膜７から分離されることなく、撥液性を有する絶縁膜４上にも位置する。そして、絶縁膜４に位置した当該後方部分においても乾燥（溶媒の揮発）が促進される。その結果、溶液２５０の溶質である有機半導体材料が析出することで、導電膜４上においても有機半導体膜７が製膜される。なお、導電膜６から見て、導電膜５が位置する側とは逆側の絶縁膜４では、溶液２５０の一部を引き延ばすための構成が存在しないため、溶液２５０の乾燥が促進されることもなく、したがって、有機半導体膜７が製膜されることもない。 As the blade 300 moves further onto the region between the conductive films 5 and 6 as shown in FIGS. 9A and 9B, 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. As a result, 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. It should be noted that 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.
　図１０Ａ及び１０Ｂに示されるようにブレード３００が導電膜６が存在しない領域上にさらに移動すると、上述のとおり、導電膜５と導電膜６の間の領域における絶縁膜４上への有機半導体膜７の製膜が進行する。ただし、溶液２５０の後方部分の左右に親液性を有する導電膜６が存在しない領域においては、溶液２５０が親液性を有する導電膜５上のみに製膜され、導電膜５と重畳しない領域における溶液２５０がブレード３００の移動に追従して移動する。 When the blade 300 further moves onto the region where the conductive film 6 does not exist as shown in FIGS. 10A and 10B, as described above, the organic semiconductor film on the insulating film 4 in the region between the conductive film 5 and the conductive film 6 The film formation of 7 proceeds. However, in the region where the conductive film 6 having positivity does not exist on the left and right of the rear portion of the solution 250, the solution 250 is formed only on the conductive film 5 having positivity and does not overlap with the conductive film 5. The solution 250 in the above moves following the movement of the blade 300.
　図１１Ａ及び１１Ｂに示されるようにブレード３００が導電膜５が存在しない領域上にさらに移動すると、溶液２５０が有機半導体膜７から分離される。以上によって、有機半導体膜７の製膜が完了する（図１Ａ及び１Ｂ参照）。 When the blade 300 further moves onto the region where the conductive film 5 does not exist as shown in FIGS. 11A and 11B, the solution 250 is separated from the organic semiconductor film 7. As a result, the formation of the organic semiconductor film 7 is completed (see FIGS. 1A and 1B).
３　変更例
　上述した半導体装置及びその製造方法は、本発明の一例であって、上述した半導体装置及びその製造方法と異なる特徴を備える半導体装置及びその製造方法も本発明に含まれる。 3 Modification Example 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.
　例えば、図１Ｂ及び３Ｂに示される下地膜２及び１３は、本発明において不可欠の構成ではない。そのため、図１２に示されるように基体１と、導電膜３及び絶縁膜４が接する半導体装置も本発明の一態様である。なお、図１Ｂ等に示される半導体装置は、上述の製造方法によって製膜されることになるため、比較的簡便な方法によって導電膜３を高精細にパターニングできる点で好ましい。他方、図１２に示される半導体装置は、下地膜２の製膜工程を削減できる点で好ましい。 For example, 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.
　また、本発明の半導体装置において最初に有機半導体膜が製膜される導電膜（図１Ａ及び１Ｂに示される導電膜６及び図３Ａ及び３Ｂに示される導電膜２３）の形状は、「コ」の字状に限定されない。例えば、当該導電膜の形状として、図１３～１５に示される導電膜２３’～２３’’’のいずれかの形状を適用することも可能である。なお、図１３～１５においては図３Ａ及び３Ｂに示される導電膜２３の変形例を示しているものの、図１Ａ及び１Ｂに示される導電膜７の形状を図１３～１５に示される導電膜２３’～２３’’’の形状に変更することもできる。 Further, in the semiconductor device of the present invention, the shape of the conductive film on which the organic semiconductor film is first formed (the conductive film 6 shown in FIGS. 1A and 1B and the conductive film 23 shown in FIGS. 3A and 3B) is "co". It is not limited to the shape of. For example, as 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. Although 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'''.
　例えば、本発明の半導体装置において最初に有機半導体膜が製膜される導電膜は、図１３に示される導電膜２３’のように、その上面形状の少なくとも一部が湾曲していてもよい。具体的には、導電膜２３’は、導電膜１９及び２１が延在する方向、すなわち、上記の第１方向及び第４方向に沿って延在する上方部分及び下方部分と、上方部分の第１方向側の末端から下方部分の第１方向側の末端まで湾曲して延在する中間部分とからなる。 For example, in the semiconductor device of the present invention, at least a part of the upper surface shape of the conductive film on which the organic semiconductor film is first formed may be curved as in the conductive film 23'shown in FIG. Specifically, 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.
　また、導電膜２３’は、図３Ａ及び４に示される導電膜２３と同様に、導電膜１９及び２１から見て、上記の第１方向に位置する第１部分２３’－１と、導電膜１９及び２１と第１部分２３’－１の間の領域から見て、上記の第２方向に位置する第２部分２３’－２及び上記の第３方向に位置する第３部分２３’－３と、第２部分２３’－２から見て、上記の第４方向に位置する第４部分２３’－４と、第３部分２３’－３から見て、上記の第４方向に位置する第５部分２３’－５とを含む。 Further, 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.
　なお、導電膜２３’における上方部分は、第２部分２３’－２の一部及び第４部分２３’－４を含む。また、導電膜２３’における下方部分は、第３部分２３’－３の一部及び第５部分２３’－５を含む。また、導電膜２３’における中間部分は、第１部分２３’－１、第２部分２３’－２の残部及び第３部分２３’－３を含む。 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.
　また、本発明の半導体装置において最初に有機半導体膜が製膜される導電膜は、図１４に示されるように、分離されている複数のサブ導電膜２３Ａ～２３Ｃを含んでいてもよい。具体的には、サブ導電膜２３Ａは、導電膜１９及び２１から見て、上記の第１方向に位置する部分２３’’－１を含む。また、サブ導電膜２３Ｂは、導電膜１９及び２１と部分２３’’－１の間の領域から見て、上記の第２方向に位置する一部と、導電膜１９から見て、上記の第２方向に位置する残部とからなる。また、サブ導電膜２３Ｃは、導電膜１９及び２１と部分２３’’－１の間の領域から見て、上記の第３方向に位置する一部と、導電膜２１から見て、上記の第３方向に位置する残部とからなる。さらに、サブ導電膜２３Ａは、サブ導電膜２３Ｂの上記の第１方向側の末端から見て、上記の第２方向に位置する部分と、サブ導電膜２３Ｃの上記の第１方向側の末端から見て、上記の第３方向に位置する部分とを含む。 Further, as shown in FIG. 14, 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. Specifically, the sub-conductive film 23A includes the portion 23 ″ -1 located in the first direction as viewed from the conductive films 19 and 21. Further, 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. Further, 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.
　また、図１４に示されるサブ導電膜２３Ａ～２３Ｃは、図３Ａ及び４に示される導電膜２３と同様に、導電膜１９及び２１から見て、上記の第１方向に位置する第１部分２３’’－１と、導電膜１９及び２１と第１部分２３’’－１の間の領域から見て、上記の第２方向に位置する第２部分２３’’－２及び上記の第３方向に位置する第３部分２３’’－３と、第２部分２３’’－２から見て、上記の第４方向に位置する第４部分２３’’－４と、第３部分２３’’－３から見て、上記の第４方向に位置する第５部分２３’’－５とを含む。 Further, 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.
　なお、図１４に示されるサブ導電膜２３Ａ～２３Ｃにおける第１部分２３’’－１は、サブ導電膜２３Ａの一部を含む。また、図１４に示されるサブ導電膜２３Ａ～２３Ｃにおける第２部分２３’’－２は、サブ導電膜２３Ａの一部及びサブ導電膜２３Ｂの一部を含む。ここで、図１４に示されているように、サブ導電膜２３Ｂの末端は、サブ導電膜２３Ａの上部側の末端よりも第３方向（図の下方）にずれた位置で第１方向に伸長することができ、これによりサブ導電膜２３Ａの一部とサブ導電膜２３Ｂの一部とが第１方向において重なり合う領域が存在することが好ましい。また、図１４に示されるサブ導電膜２３Ａ～２３Ｃにおける第３部分２３’’－３は、サブ導電膜２３Ａの一部及びサブ導電膜２３Ｃの一部を含む。ここで、図１４に示されているように、サブ導電膜２３Ｃの末端は、サブ導電膜２３Ａの下部側の末端よりも第２方向（図の上方）にずれた位置で第１方向に伸長することができ、これによりサブ導電膜２３Ａの一部とサブ導電膜２３Ｃの一部とが第１方向において重なり合う領域が存在することが好ましい。また、図１４に示されるサブ導電膜２３Ａ～２３Ｃにおける第４部分２３’’－４は、サブ導電膜２３Ｂの残部を含む。また、図１４に示されるサブ導電膜２３Ａ～２３Ｃにおける第５部分２３’’－５は、サブ導電膜２３Ｃの残部を含む。 Note that 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. Further, 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. Here, as shown in FIG. 14, 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. Further, 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. Here, as shown in FIG. 14, 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. Further, 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. Further, 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.
　また、図１４においては、最初に有機半導体膜が製膜される導電膜が３つのサブ導電膜２３Ａ～２３Ｃからなる場合の一例を示したが、サブ導電膜の個数は２又は４以上でもよい。この場合、上記の第１部分乃至第５部分の少なくとも一つは、複数のサブ導電膜のうちの少なくとも２つのサブ導電膜それぞれの少なくとも一部を含むことになる。 Further, in FIG. 14, an example is shown in which 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. .. In this case, 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.
　また、本発明の半導体装置において最初に有機半導体膜が製膜される導電膜は、図１５に示される導電膜２３’’’のように、一端部２３’’’－６及び他端部２３’’’－７が、上記の第２方向及び第３方向において導電膜１９及び２１と重畳しないように延在していてもよい。なお、図４Ｂ等に示される導電膜２３を有する半導体装置は、図１５に示される導電膜２３’’’を有する半導体装置と比較して、導電膜１９及び２１に生じる寄生容量を低減することができる点で好ましい。他方、図１５に示される導電膜２３’’’を有する半導体装置は、図４等に示される導電膜２３を有する半導体装置と比較して、トランジスタのチャネル形成領域となる導電膜１９と導電膜２１の間の領域に有機半導体膜２５を確実に製膜することが可能となる点で好ましい。 Further, in the semiconductor device of the present invention, 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. On the other hand, 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.
　また、本発明の半導体装置においては、下地膜２又は１３及び導電膜３又は１５を公知のフォトリソグラフィ工程を用いて製膜してもよい。なお、上述の製膜方法によって下地膜２又は１３及び導電膜３又は１５を製膜する場合には、比較的簡便な方法によって導電膜３又は１５を高精細にパターニングできることができる点で好ましい。他方、公知のフォトリソグラフィ工程を用いる場合には、材料選択の自由度等が増加する、すなわち、それぞれに適した材料をより広い選択肢の中から選択することが可能となる点で好ましい。 Further, in the semiconductor device of the present invention, the undercoat film 2 or 13 and the conductive film 3 or 15 may be formed by using a known photolithography step. When the undercoat film 2 or 13 and the conductive film 3 or 15 are formed by the above-mentioned film forming method, the conductive film 3 or 15 can be patterned with high definition by a relatively simple method, which is preferable. On the other hand, 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.
　また、本発明の半導体装置においては、導電膜５及び６又は導電膜１９、膜２１及び２３を同一の工程によって製膜してもよいし、異なる工程で製膜してもよい。なお、これらを同一の工程で製膜する場合には、半導体装置の製膜工程を削減できる点で好ましい。他方、これらを異なる工程で製膜する場合には、材料選択の自由度が増加する点で好ましい。 Further, in the semiconductor device of the present invention, 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.
図３Ａ及び３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置の製造
　図３Ａ及び図３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置を製造した。まず、基体として、ＳｉＯ２熱酸化膜（１００ｎｍ）付きシリコンウェハーを用意し、基体上に下地膜となるＡＧＣ社製ＣＹＴＯＰ　ＣＴＬ８０９Ｍ（登録商標）をスピンコート法により、厚さ約２５ｎｍとなるように塗布製膜した。次いで、シャドウマスクを介して導電膜の材料である金（Ａｕ）を蒸着により厚さ２５ｎｍとなるように製膜した。次いで、導電膜の表面をペンタフルオロベンゼンチオールの蒸気に２０分間暴露した。次いで、下記の公知有機半導体材料であるＮｏ．１及びＮｏ．２を、質量濃度が０．０５％となるようにそれぞれクロロベンゼンに溶解したのち、Ｎｏ．１：Ｎｏ．２＝９：１の体積比率で混合した。。次いで、得られた溶液を、上記の基体にガラスブレードを用いて３．５μｍ／秒の速度でブレードコートし、室温で乾燥することで、必要な箇所にのみ半導体膜が製膜された有機半導体装置を製造した。なお、ガラスブレードは、ＡＧＣ社製ＣＹＴＯＰ　ＣＴＬ８０９Ｍ（登録商標）によりコーティング処理されている。また、得られた有機半導体膜の膜厚は、約５ｎｍであった。 Manufacture of a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B A semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was manufactured . .. First, 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. Next, gold (Au), which is a material for the conductive film, was formed by vapor deposition through a shadow mask so as to have a thickness of 25 nm. The surface of the conductive film was then exposed to vapor of pentafluorobenzenethiol for 20 minutes. Next, No. 1 which is the following known organic semiconductor material. 1 and No. No. 2 was dissolved in chlorobenzene so that the mass concentration was 0.05%, and then No. 1: No. The mixture was mixed at a volume ratio of 2 = 9: 1. .. Next, the obtained solution was blade-coated on the above-mentioned substrate at a rate of 3.5 μm / 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. Manufactured the device. 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.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　偏光顕微鏡を用いたクロスニコル観察により得られた半導体装置の写真を図１６に示す。クロスニコル観察による色の明滅から結晶性の有機半導体薄膜が製膜された領域を決定したところ、図中、点線で示した領域の外におけるＣＹＴＯＰ上では有機半導体膜が製膜されていることを示す色の明滅は観察されず、有機半導体膜が製膜されていないことが確認できた。一方で、点線で示した導電膜に囲まれた領域では、複数の結晶方位を持つ結晶性の高い有機半導体薄膜が欠損なく製膜されていることが確認できた。 FIG. 16 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, 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. 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.
実施例１に記載の有機半導体装置の評価
　実施例１により製造した半導体装置に含まれるチャネル幅８００μｍ及びチャネル長１００μｍのソース電極およびドレイン電極で構成される有機薄膜トランジスタ素子の有機薄膜トランジスタ特性を測定した。なお、本有機薄膜トランジスタ素子では、熱酸化膜層となるＳｉＯ２および下地膜となるＡＧＣ社製ＣＹＴＯＰ　ＣＴＬ８０９Ｍ（登録商標）が絶縁膜の役割を果たし、そのキャパシタンスは２４ｎＦ／ｃｍ２として素子特性値を算出した。得られた半導体装置に含まれる有機薄膜トランジスタ素子の出力特性を図１７に示す。図１７に示されるとおり、当該有機薄膜トランジスタ素子は、典型的なトランジスタ素子と同様に線形・飽和の出力特性を示した。また、図１８に示されるとおり、当該薄膜トランジスタにおいては、２Ｖ以下の低電圧駆動が可能であるとともにそのヒステリシスも小さかった。閾値電圧近傍においてドレイン電流が急激に変化することを示すサブスレショルドスイング値を算出したところ、その値は６７ｍＶ／ｄｅｃとなり、理論限界に迫るきわめて急峻なスイッチング特性を示した。また、当該有機薄膜トランジスタ素子のキャリア移動度を算出したところ、最大で４．４ｃｍ２／Ｖｓの高移動度を示した。 Evaluation of Organic Semiconductor Device Described in 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 μm and a channel length of 100 μm included in the semiconductor device manufactured in Example 1 were measured. In this organic thin film transistor element, 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. 17, 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.
図１Ａ及び１Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置の製造
　ソース及びドレインとして機能する導電膜を形成するために必要なシャドウマスクの形状を変えた以外は実施例１に記載の方法と同様の方法により、半導体装置の製造を行った。得られた半導体装置の偏光顕微鏡写真を図１９に示す。実施例１に記載の方法と同様の方法により、有機半導体膜が製膜されている箇所を確認したところ、図中、点線で示された導電膜に囲まれた領域のみに結晶性の有機半導体薄膜が得られる結果となった。 Examples except that the shape of the shadow mask required to form a conductive film that functions as a production source and drain of a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 1A and 1B is changed. 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. When the location where the organic semiconductor film was formed was confirmed by the same method as that described in Example 1, 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.
実施例３に記載の有機半導体装置の評価
　実施例３により製造した半導体装置に含まれるチャネル幅３００μｍ及びチャネル長５０μｍのソース電極およびドレイン電極で構成される有機薄膜トランジスタ素子の有機薄膜トランジスタ特性を測定した。なお、本有機薄膜トランジスタ素子における絶縁膜及びキャパシタンスは実施例２に記載の膜及び値と同様である。得られた半導体装置に含まれる有機薄膜トランジスタ素子の出力特性を図２０に示す。図２０に示されるとおり、当該有機薄膜トランジスタ素子は、典型的なトランジスタ素子と同様に線形・飽和の出力特性を示した。また、図２１に示されるとおり、当該薄膜トランジスタにおいては、２Ｖ以下の低電圧駆動が可能であるとともにそのヒステリシスも小さかった。閾値電圧近傍においてドレイン電流が急激に変化することを示すサブスレショルドスイング値を算出したところ、その値は７５ｍＶ／ｄｅｃとなり、きわめて急峻なスイッチング特性を示した。また、当該有機薄膜トランジスタ素子のキャリア移動度を算出したところ、最大で１．０ｃｍ２／Ｖｓの高移動度を示した。 Evaluation of Organic Semiconductor Device Described in 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 μm and a channel length of 50 μm 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. 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 75 mV / dec, showing an extremely steep switching characteristic. Moreover, when 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.
実施例１に記載の有機半導体装置のばらつき評価
　実施例１により製造した半導体装置に含まれるチャネル幅８００μｍ及びチャネル長１００μｍのソース電極およびドレイン電極で構成される有機薄膜トランジスタ素子の有機薄膜トランジスタ特性の特性ばらつきを評価した。ドレイン電圧Ｖｄを－０．２Ｖおよび－２．０Ｖとした場合の移動度、サブスレッショルドスイング（ＳＳ）値およびトランジスタをスイッチングさせるのに必要な閾値電圧の値とそのばらつきを評価した結果を以下の表１に示す。
[表１]
Figure JPOXMLDOC01-appb-I000006
 Evaluation of Variations in Organic Semiconductor Devices Described in Example 1 Characteristics of Organic Thin Film Transistor Elements Consists of Source and Drain Electrodes with a Channel Width of 800 μm and a Channel Length of 100 μm 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]
Figure JPOXMLDOC01-appb-I000006
　測定したすべての素子で高い移動度、高急峻なスイッチング特性をきわめて小さい閾値電圧で示し、それらのばらつきはいずれも小さい値を示した。以上の結果から、本発明により得られる素子は高移動度かつ急峻なスイッチング特性を低電圧かつ優れた歩留まりで作成可能なことがわかった。 All the measured elements showed high mobility and high steep switching characteristics with extremely small threshold voltage, and their variations showed small values. From the above results, it was found that the device obtained by the present invention can produce high mobility and steep switching characteristics with low voltage and excellent yield.
図３Ａ及び３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置の製造
　公知文献（特開２０１４１９５７９４、Ｎａｔｕｒｅ　Ｃоｍｍｕｎ．２０１６、７、１１４０２－１－９）に記載の方法によって、銀ナノインクを用いて印刷プロセスによって形成したゲート電極、ソース電極およびドレイン電極を有する、図３Ａ及び図３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置を製造した。まず、基体としてガラス基板を用意し、基体上に下地膜となるＡＧＣ社製ＣＹＴＯＰ　ＣＴＬ８０９Ｍ（登録商標）をスピンコート法により塗布製膜した。次いで、フォトマスクを介してＶＵＶ光をパターン照射後、上記公知文献（Ｎａｔｕｒｅ　Ｃоｍｍｕｎ．２０１６、７、１１４０２－１－９）に記載の銀ナノ粒子を含むインクを、同公知文献に記載のブレードコート法により製膜し、銀ナノ粒子からなるゲート電極を作製した。次いで、上記と同様の方法でＣＹＴＯＰ　ＣＴＬ８０９Ｍをスピンコート法により塗布製膜した後、実施例１に記載の方法と同様の方法でペンタフルオロベンゼンチオールを気相処理し、上記と同様の方法で銀ナノ粒子からなるソース電極、ドレイン電極およびガイド電極を作製した。次ぐ半導体層の製膜は、実施例１に記載の半導体材料を、実施例１に記載した方法と同様の方法によって製膜し、必要な箇所にのみ半導体膜が製膜された有機半導体装置を製造した。当該有機半導体装置の半導体層の製膜状況をより明確に観察するために、酸化膜付きシリコン基板上に前記方法と同様の方法によってＣＹＴＯＰ層および銀ナノ粒子からなるソースおよびドレイン電極層を形成した基体に、上記の方法と同様に有機半導体層をパターン製膜した、すなわち前記半導体装置と同条件下にて半導体層製膜が施されている有機半導体装置の、偏光顕微鏡を用いたクロスニコル観察により得られた半導体装置の写真を図２２に示す。クロスニコル観察による色の明滅から結晶性の有機半導体薄膜が製膜された領域を決定したところ、図中、黒点線で示した領域の外におけるＣＹＴＯＰ上では有機半導体膜が製膜されていることを示す色の明滅は観察されず、有機半導体膜が製膜されていないことが確認できた。一方で、点線で示した導電膜に囲まれた領域では、複数の結晶方位を持つ結晶性の高い有機半導体薄膜が欠損なく製膜されていることが確認できた。 According to the method described in a known document for manufacturing a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B (Japanese Patent Laid-Open No. 2014195794, Nature Cоmmun. 2016, 7, 11402-1-9). 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. First, 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. Next, after pattern irradiation with VUV light via a photomask, an ink containing silver nanoparticles described in the above-mentioned known document (Nature Cоmmun. 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. Next, 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. Next, 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. Manufactured. In order to more clearly observe the film-forming state of the semiconductor layer of the organic semiconductor device, 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. Cross Nicole observation using a polarization microscope of an organic semiconductor device in which an organic semiconductor layer is patterned on a substrate in the same manner as in the above method, that is, the semiconductor layer is formed under the same conditions as the semiconductor device. A photograph of the semiconductor device obtained in FIG. 22 is shown in FIG. 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 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.
実施例６に記載の有機半導体装置の評価
　実施例６により製造した半導体装置に含まれるチャネル幅８００μｍ及びチャネル長２００μｍのソース電極およびドレイン電極で構成される有機薄膜トランジスタ素子の有機薄膜トランジスタ特性を測定した。なお、本有機薄膜トランジスタ素子では、絶縁膜の役割を果たすＣＹＴＯＰ　ＣＴＬ８０９Ｍ層のキャパシタンスは実験的に得られた値をもとに算出し、２．９ｎＦ／ｃｍ２として素子特性値を算出した。当該有機薄膜トランジスタ素子は、実施例１に記載したトランジスタ素子と同様に有機電界効果トランジスタに典型的な線形・飽和の出力・伝達特性の形状をヒステリシスなく示した。得られた特性から当該有機薄膜トランジスタ素子のキャリア移動度を算出したところ、低電圧駆動下において（ドレイン電圧Ｖｄ＝－０．５Ｖ）最大で２．０ｃｍ２／Ｖｓの高移動度を示した。また、閾値電圧近傍においてドレイン電流が急激に変化することを示すサブスレショルドスイング（ＳＳ）値を算出したところ、その値は１７０ｍＶ／ｄｅｃとなり、きわめて急峻なスイッチング特性を示した。 Evaluation of Organic Semiconductor Device Described in 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 μm and a channel length of 200 μm included in the semiconductor device manufactured in Example 6 were measured. In this organic thin film transistor device, 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. Similar to the transistor element described in Example 1, the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis. When the carrier mobility of the organic thin film transistor element was calculated from the obtained characteristics, it showed a high mobility of 2.0 cm 2 / Vs at the maximum under low voltage drive (drain voltage Vd = −0.5 V). Further, when the sub-threshold swing (SS) value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 170 mV / dec, showing an extremely steep switching characteristic.
図３Ａ及び３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置の製造
　実施例１に記載の方法に対して、導電膜である金電極の作製を実施例７に記載の印刷プロセスを用いた銀ナノ粒子による作製に変え、半導体層作製に使用する半導体溶液を下記の公知有機半導体材料であるＮｏ．３及びＮｏ．４を質量濃度が０．０５％となるようにそれぞれクロロベンゼンに溶解したのち、Ｎｏ．３：Ｎｏ．４＝９：１の体積比率で混合した溶液に変えた以外は実施例１に記載の方法と同様の方法で、図３Ａ及び図３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置を製造した。
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
 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. Instead of manufacturing with silver nanoparticles using a printing process, 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. A conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was prepared by the same method as that described in Example 1 except that the solution was changed to a mixed solution at a volume ratio of 4 = 9: 1. Manufactured semiconductor devices including.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
　偏光顕微鏡を用いたクロスニコル観察により得られた半導体装置の写真を図２３に示す。クロスニコル観察による色の明滅から結晶性の有機半導体薄膜が製膜された領域を決定したところ、図中、黒点線で示した領域の外におけるＣＹＴＯＰ上では有機半導体膜が製膜されていることを示す色の明滅は観察されず、有機半導体膜が製膜されていないことが確認できた。一方で、点線で示した導電膜に囲まれた領域では、複数の結晶方位を持つ結晶性の高い有機半導体薄膜が欠損なく製膜されていることが確認できた。 FIG. 23 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 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.
実施例８に記載の有機半導体装置の評価
　実施例８により製造した半導体装置に含まれるチャネル幅８００μｍ及びチャネル長８０μｍのソース電極およびドレイン電極で構成される有機薄膜トランジスタ素子の有機薄膜トランジスタ特性を測定した。なお、本有機薄膜トランジスタ素子では、熱酸化膜層となるＳｉＯ２および下地膜となるＣＹＴＯＰ　ＣＴＬ８０９Ｍが絶縁膜の役割を果たし、そのキャパシタンスは２．５ｎＦ／ｃｍ２として素子特性値を算出した。当該有機薄膜トランジスタ素子は、実施例１に記載したトランジスタ素子と同様に有機電界効果トランジスタに典型的な線形・飽和の出力・伝達特性の形状をヒステリシスなく示した。合計１５素子の測定を行い、得られた特性から当該有機薄膜トランジスタ素子のキャリア移動度を算出したところ、低電圧駆動化において（ドレイン電圧Ｖｄ＝－５Ｖ）平均０．２９ｃｍ２／Ｖｓの移動度を示した。また、閾値電圧近傍においてドレイン電流が急激に変化することを示すサブスレショルドスイング（ＳＳ）値を算出したところ、その値は２３０±４０ｍＶ／ｄｅｃとなり、きわめて急峻なスイッチング特性を小さなばらつきで示した。 Evaluation of Organic Semiconductor Device Described in 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 μm and a channel length of 80 μm included in the semiconductor device manufactured in Example 8 were measured. In this organic thin film transistor element, 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. Similar to the transistor element described in Example 1, the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis. Total 15 performs measurement of element, where the resulting characteristics were calculated carrier mobility of the organic thin-film transistor element, in the low-voltage driving (the drain voltage Vd = -5V) mobility of average 0.29 cm 2 / Vs Indicated. Further, when the sub-threshold swing (SS) value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 230 ± 40 mV / dec, and an extremely steep switching characteristic was shown with a small variation.
図３Ａ及び３Ｂに示される導電膜２３のみを持つ半導体装置の製造
　本発明により製造される半導体デバイス装置に含まれる、コの字の電極パターンを有する基板に対し、ブレードコート法による製膜によって半導体薄膜が形成可能かどうかの検証を行った。酸化膜付シリコン基板に下地膜となるＣＹＴＯＰ　ＣＴＬ８０９Ｍをスピンコート法により塗布製膜し、次いでフォトマスクを介してＶＵＶ光をパターン照射後、銀ナノ粒子を含むインクをブレードコート法により製膜し、銀ナノ粒子からなる導電膜を作製した。この基板に、実施例８に記載の方法と同様の方法で半導体薄膜を製膜した。得られた結果を図２４に示す。図中、黒点線で示した領域内にのみ半導体薄膜が形成されており、本発明による導電膜の配置によって半導体がパターニング製膜できることが確認できた。 Manufacture of Semiconductor Device with Only Conductive 23 shown in FIGS. 3A and 3B 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.
図３Ａ及び３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置の製造
　実施例１に記載の方法に対して、半導体層作製に使用する半導体溶液を下記の公知有機半導体材料であるＮｏ．５に変えた以外は実施例１に記載の方法と同様の方法で、図３Ａ及び図３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置を製造した。
Figure JPOXMLDOC01-appb-C000009
 For the method according to 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, 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.
Figure JPOXMLDOC01-appb-C000009
　偏光顕微鏡を用いたクロスニコル観察により得られた半導体装置の写真を図２５に示す。クロスニコル観察による色の明滅から結晶性の有機半導体薄膜が製膜された領域を決定したところ、図中、黒点線で示した領域の外におけるＣＹＴＯＰ上では有機半導体膜が製膜されていることを示す色の明滅は観察されず、有機半導体膜が製膜されていないことが確認できた。一方で、点線で示した導電膜に囲まれた領域では、複数の結晶方位を持つ結晶性の高い有機半導体薄膜が欠損なく製膜されていることが確認できた。 FIG. 25 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 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.
実施例１１に記載の有機半導体装置の評価
　実施例１１により製造した半導体装置に含まれるチャネル幅８００μｍ及びチャネル長１００μｍのソース電極およびドレイン電極で構成される有機薄膜トランジスタ素子の有機薄膜トランジスタ特性を測定した。なお、本有機薄膜トランジスタ素子では、熱酸化膜層となるＳｉＯ２および下地膜となるＣＹＴＯＰ　ＣＴＬ８０９Ｍが絶縁膜の役割を果たし、そのキャパシタンスは２３ｎＦ／ｃｍ２として素子特性値を算出した。当該有機薄膜トランジスタ素子は、実施例１に記載したトランジスタ素子と同様に有機電界効果トランジスタに典型的な線形・飽和の出力・伝達特性の形状をヒステリシスなく示した。得られた特性から当該有機薄膜トランジスタ素子のキャリア移動度を算出したところ、低電圧駆動下において（ドレイン電圧Ｖｄ＝－０．５Ｖ）最大４．４ｃｍ２／Ｖｓの移動度を示した。また、閾値電圧近傍においてドレイン電流が急激に変化することを示すサブスレショルドスイング（ＳＳ）値を算出したところ、その値は最小で８９ｍＶ／ｄｅｃとなり、きわめて急峻なスイッチング特性を示した。 Evaluation of Organic Semiconductor Device Described in 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 μm and a channel length of 100 μm included in the semiconductor device manufactured according to Example 11 were measured. In this organic thin film transistor element, 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. Similar to the transistor element described in Example 1, the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis. When the carrier mobility of the organic thin film transistor element was calculated from the obtained characteristics, it showed a maximum mobility of 4.4 cm 2 / Vs under low voltage drive (drain voltage Vd = −0.5 V). Further, when the sub-threshold swing (SS) value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 89 mV / dec at the minimum, showing an extremely steep switching characteristic.
図３Ａ及び３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置の製造
　実施例１に記載の方法に対して、半導体層作製に使用する半導体溶液を実施例１１に記載の有機半導体材料であるＮｏ．５と下記の公知の有機半導体材料Ｎｏ．６を質量濃度が０．０５％となるようにそれぞれクロロベンゼンに溶解したのち、Ｎｏ．５：Ｎｏ．６＝８：２の体積比率で混合した溶液に変えた以外は実施例１に記載の方法と同様の方法で、図３Ａ及び図３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置を製造した。
Figure JPOXMLDOC01-appb-C000010
 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, a semiconductor solution used for producing a semiconductor layer is described in Example 11. No. which is an organic semiconductor material. 5 and the following known organic semiconductor material No. No. 6 was dissolved in chlorobenzene so that the mass concentration was 0.05%, and then No. 5: No. A conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was prepared by the same method as that described in Example 1 except that the solution was changed to a mixed solution at a volume ratio of 6 = 8: 2. Manufactured semiconductor devices including.
Figure JPOXMLDOC01-appb-C000010
　偏光顕微鏡を用いたクロスニコル観察により得られた半導体装置の写真を図２６に示す。なお、該実施例における導電膜のパターンは実施例１で用いた図１６に示したものと同形のものを用いており、図２５に示す写真は半導体デバイスとして機能するソース電極部およびドレイン電極部を拡大したものである。クロスニコル観察による色の明滅から結晶性の有機半導体薄膜が製膜された領域を決定したところ、図中、黒点線で示した領域の外におけるＣＹＴＯＰ上では有機半導体膜が製膜されていることを示す色の明滅は観察されず、有機半導体膜が製膜されていないことが確認できた。一方で、点線で示した導電膜に囲まれた領域では、複数の結晶方位を持つ結晶性の高い有機半導体薄膜が欠損なく製膜されていることが確認できた。 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. 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 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.
実施例１３に記載の有機半導体装置の評価
　実施例１３により製造した半導体装置に含まれるチャネル幅８００μｍ及びチャネル長２００μｍのソース電極およびドレイン電極で構成される有機薄膜トランジスタ素子の有機薄膜トランジスタ特性を測定した。なお、本有機薄膜トランジスタ素子では、熱酸化膜層となるＳｉＯ２および下地膜となるＣＹＴＯＰ　ＣＴＬ８０９Ｍが絶縁膜の役割を果たし、そのキャパシタンスは２３ｎＦ／ｃｍ２として素子特性値を算出した。当該有機薄膜トランジスタ素子は、実施例１に記載したトランジスタ素子と同様に有機電界効果トランジスタに典型的な線形・飽和の出力・伝達特性の形状をヒステリシスなく示した。得られた特性から当該有機薄膜トランジスタ素子のキャリア移動度を算出したところ、低電圧駆動下において（ドレイン電圧Ｖｄ＝－０．５Ｖ）最大０．７９ｃｍ２／Ｖｓの移動度を示した。また、閾値電圧近傍においてドレイン電流が急激に変化することを示すサブスレショルドスイング（ＳＳ）値を算出したところ、その値は７０ｍＶ／ｄｅｃとなり、きわめて急峻なスイッチング特性を示した。 Evaluation of Organic Semiconductor Device Described in 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 μm and a channel length of 200 μm included in the semiconductor device manufactured according to Example 13 were measured. In this organic thin film transistor element, 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. Similar to the transistor element described in Example 1, the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis. When the carrier mobility of the organic thin film transistor element was calculated from the obtained characteristics, it showed a maximum mobility of 0.79 cm 2 / Vs under low voltage drive (drain voltage Vd = −0.5 V). Further, when the sub-threshold swing (SS) value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 70 mV / dec, showing an extremely steep switching characteristic.
図３Ａ及び３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置の製造
　実施例１に記載の方法に対して、半導体層作製に使用する半導体溶液を市販の有機半導体材料であるポリ（３－ヘキシル）チオフェン（メルク社製）のクロロベンゼン溶液に変え、５．０μｍ／秒の速度で半導体溶液をブレードコート製膜した以外は実施例１に記載の方法と同様の方法で、図３Ａ及び図３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置を製造した。顕微鏡を用いた観察により得られた半導体装置の写真を図２７に示す。ポリ（3－ヘキシル）チオフェンは当該基板上で薄膜を形成する場合、橙色に観察されるため、製膜された部位を容易に観測することができる。図中、黒点線で示した領域の外におけるＣＹＴＯＰ上では有機半導体膜が製膜されておらず、一方で、点線で示した導電膜に囲まれた領域では、ポリ（3－ヘキシル）チオフェンが欠損なく製膜されていることを確認できた。 For the method according to 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, 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 μm / 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. When a thin film is formed on the substrate, poly (3-hexyl) thiophene is observed in orange, so that the formed portion can be easily observed. In the figure, the organic semiconductor film is not formed on the CYTOP outside the region shown by the black dotted line, while the poly (3-hexyl) thiophene is formed in the region surrounded by the conductive film shown by the dotted line. It was confirmed that the film was formed without any defects.
図３Ａ及び３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置の製造
　実施例１に記載の方法に対して、ＳｉＯ２熱酸化膜（１００ｎｍ）付きシリコンウェハーにＣＹＴＯＰの製膜は行わず、代わりに１Ｈ，１Ｈ，２Ｈ，２Ｈ，－パーフルオロデシルトリエトキシラン（ＦＡＳ－１７、メルク社製）の蒸気を１２０℃下にて暴露することで基板表面修飾による撥液処理を行い、１．５μｍ／秒の速度で半導体溶液をブレードコート製膜した以外は実施例１に記載の方法と同様の方法で図３Ａ及び図３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置を製造した。偏光顕微鏡を用いたクロスニコル観察により得られた半導体装置の写真を図２８に示す。クロスニコル観察による色の明滅から結晶性の有機半導体薄膜が製膜された領域を決定したところ、図中、点線で示した領域の外におけるＣＹＴＯＰ上では有機半導体膜が製膜されていることを示す色の明滅は観察されず、有機半導体膜が製膜されていないことが確認できた。一方で、点線で示した導電膜に囲まれた領域では、複数の結晶方位を持つ結晶性の高い有機半導体薄膜が欠損なく製膜されていることが確認できた。 For the process described in preparation example 1 of the semiconductor device including a conductive film having a corresponding shape to the conductive film 23 shown in FIGS. 3A and 3B, manufacturing of CYTOP silicon wafer with SiO 2 thermal oxide film (100 nm) No film is formed, and instead, liquid repellent treatment by surface modification of the substrate is performed by exposing the vapor of 1H, 1H, 2H, 2H, -perfluorodecyltriethoxylan (FAS-17, manufactured by Merck) at 120 ° C. 3A and 3B have a shape corresponding to the conductive film 23 shown in FIGS. A semiconductor device including a conductive film was manufactured. FIG. 28 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, 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. 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.
図３Ａ及び３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置の製造
　実施例１に記載の方法に対して、半導体溶液の調液に使用する溶媒をо－キシレンに変え、Ａｕ電極のＰＦＢＴ蒸気暴露は行わず、２．０μｍ／秒の速度で半導体溶液をブレードコート製膜した以外は実施例１に記載の方法と同様の方法で図３Ａ及び図３Ｂに示される導電膜２３に対応する形状を備える導電膜を含む半導体装置を製造した。偏光顕微鏡を用いたクロスニコル観察により得られた半導体装置の写真を図２９に示す。クロスニコル観察による色の明滅から結晶性の有機半導体薄膜が製膜された領域を決定したところ、図中、点線で示した領域の外におけるＣＹＴＯＰ上では有機半導体膜が製膜されていることを示す色の明滅は観察されず、有機半導体膜が製膜されていないことが確認できた。一方で、点線で示した導電膜に囲まれた領域では、複数の結晶方位を持つ結晶性の高い有機半導体薄膜が欠損なく製膜されていることが確認できた。 Manufacturing of a Semiconductor Device Containing a Conductive Included with a Conductive Conductor having a Shape Corresponding to the Conductive Conductor 23 shown in FIGS. , Au electrode was not exposed to PFBT steam, and the conductivity shown in FIGS. 3A and 3B was formed in the same manner as in Example 1 except that the semiconductor solution was blade-coated at a rate of 2.0 μm / sec. A semiconductor device including a conductive film having a shape corresponding to the film 23 was manufactured. FIG. 29 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, 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. 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.
導電膜および半導体膜の下地となる膜の濡れ性の評価
　実施例１、３、１１、１３、１５、１６に用いた導電膜であるペンタフルオロベンゼンチオール処理を施した金膜の表面エネルギー、実施例１，３，６、７、９、１１、１３、１５、１７に用いた半導体層の下地となるＣＹＴＯＰ　ＣＴＬ８０９Ｍの絶縁膜層表面エネルギー、実施例１６に用いたＦＡＳ－１７による表面処理を行った熱酸化膜付シリコン基板の表面エネルギー、および実施例１７に用いた導電膜である金膜の表面エネルギーの評価として、水およびクロロベンゼンの液滴を表面に滴下した際の接触角の測定を行った。その結果を表２に示す。
[表２]
Figure JPOXMLDOC01-appb-I000011
 Evaluation of wettability of the conductive film and the film underlying the semiconductor film The surface energy of the gold film subjected to the pentafluorobenzene thiol treatment, which is the conductive film used in Examples 1, 3, 11, 13, 15 and 16, was carried out. The surface energy of the insulating film layer of CYTOP CTL809M, which is the base of the semiconductor layer used in Examples 1, 3, 6, 7, 9, 11, 13, 15, and 17, and the surface treatment by FAS-17 used in Example 16 are performed. As an evaluation of the surface energy of the silicon substrate with a thermal oxide film and the surface energy of the gold film which is the conductive film used in Example 17, the contact angle when water and chlorobenzene droplets were dropped on the surface was measured. rice field. The results are shown in Table 2.
[Table 2]
Figure JPOXMLDOC01-appb-I000011
　実施例において半導体溶液に使用した有機溶媒であるクロロベンゼンおよびо－キシレンの接触角の値は、前記実施例における導電膜と半導体層の下地との組み合わせのすべてにおいて、導電膜よりも下地となる絶縁膜表面の方が大きな値を示した。また、水接触角の関係性も前期と同様の結果となった。 The value of the contact angle of the organic solvents chlorobenzene and о-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. In addition, the relationship between the water contact angles was the same as in the previous term.
比較例１Comparative Example 1
図３Ａ及び３Ｂに示される導電膜２３に対応する形状を備えない導電膜を含む半導体装置の製造
　実施例１に記載の方法に対して、図３Ａ及び３Ｂに示される導電膜２３に対応する形状を備えず、図３Ａ及び３Ｂに示される導電膜１９および２１のみを備えるようにして導電膜を製膜した以外は、実施例１に記載の方法と同様の方法で半導体装置を製造した。偏光顕微鏡を用いたクロスニコル観察により得られた半導体装置の写真を図３０に示す。クロスニコル観察による色の明滅から結晶性の有機半導体薄膜が製膜された領域を決定したところ、図２９右の点線で示した領域の外におけるＣＹＴＯＰ上では有機半導体膜が製膜されていることを示す色の明滅は観察されなかった。一方で、点線で示した導電膜上にのみ有機半導体薄膜が製膜されていた。従って、導電膜の一方をソース電極、他方をドレイン電極とした半導体装置におけるチャネル領域には有機半導体薄膜を製造することはできず、半導体装置を作製することは出来なかった。 Manufacturing of a Semiconductor Device Containing a Conductive Material Not Included a Shape Corresponding to a Conductive Film 23 Shown in 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. 29. No flickering of the color indicating was observed. On the other hand, 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.
１、１１：基体、２、１３：下地膜、３、１５：導電膜、１５０：溶液、４、１７：絶縁膜、５、６、１９、２１、２３、２３’、２３’’’：導電膜、６－１、２３－１、２３’－１、２３’’－１：第１部分、６－２、２３－２、２３’－２、２３’’－２：第２部分、６－３、２３－３、２３’－３、２３’’－３：第３部分、６－４、２３－４、２３’－４、２３’’－４：第４部分、６－５、２３－５、２３’－５、２３’’－５：第５部分、２３Ａ～２３Ｃ：サブ導電膜、２３’’’－６：一端部、２３’’’－７：他端部、７、２５：有機半導体膜、８－１～８－３、３０－１～３０－３：領域、２００、３００：ブレード、２５０：溶液 1,11: Substrate, 2,13: Underlayer film, 3,15: Conductive film, 150: Solution, 4,17: Insulating film, 5,6,19,21,23,23', 23''': Conductive Membrane, 6-1, 23-1, 23'-1, 23 "-1: 1st part, 6-2, 23-2, 23'-2, 23" -2: 2nd part, 6- 3, 23-3, 23'-3, 23''-3: 3rd part, 6-4, 23-4, 23'-4, 23''-4: 4th part, 6-5, 23- 5, 23'-5, 23''-5: 5th part, 23A-23C: Sub-conductive film, 23'''-6: One end, 23'''-7: Other end, 7, 25: Organic semiconductor film, 8-1 to 8-3, 30-1 to 30-3: region, 200, 300: blade, 250: solution

Claims (21)

  1. 　第１導電膜と、
    　前記第１導電膜上の絶縁膜と、
    　前記絶縁膜上の第２導電膜及び第３導電膜と、
    　前記絶縁膜、前記第２導電膜及び前記第３導電膜上の有機半導体膜とを含み、
    　前記第２導電膜は、第１方向に沿って延在する部分を含み、
    　前記第３導電膜は、
    　　前記第２導電膜から見て、前記第１方向に位置する第１部分と、
    　　前記第２導電膜と前記第１部分の間の領域から見て、前記第１方向と直交する第２方向に位置する第２部分及び前記第２方向の反対方向である第３方向に位置する第３部分と、
    　　前記第２部分から見て、前記第１方向の反対方向である第４方向に位置する第４部分と、
    　　前記第３部分から見て、前記第４方向に位置する第５部分とを含み、
    　前記第１部分、前記第２部分の少なくとも一部及び前記第３部分の少なくとも一部は、連続して延在し、
    　前記絶縁膜の表面自由エネルギーは、前記第２導電膜の表面自由エネルギー及び前記第３導電膜の表面自由エネルギーよりも小さい、半導体装置。     With the first conductive film
    The insulating film on the first conductive film and
    The second conductive film and the third conductive film on the insulating film,
    The insulating film, the second conductive film, and the organic semiconductor film on the third conductive film are included.
    The second conductive film includes a portion extending along the first direction.
    The third conductive film is
    The first portion located in the first direction when viewed from the second conductive film, and
    Seen from the region between the second conductive film and the first portion, it is located in the second portion located in the second direction orthogonal to the first direction and in the third direction opposite to the second direction. Part 3 and
    A fourth portion located in the fourth direction, which is the opposite direction of the first direction when viewed from the second portion,
    Includes a fifth portion located in the fourth direction as viewed from the third portion.
    The first part, at least a part of the second part, and at least a part of the third part are continuously extending.
    A semiconductor device in which 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.
  2. 　前記第３導電膜は、
    　　前記第１方向及び前記第４方向に沿って延在し、前記第２部分及び前記第４部分を含む上方部分と、
    　　前記第１方向及び前記第４方向に沿って延在し、前記第３部分及び前記第５部分を含む下方部分と、
    　　前記第２方向及び前記第３方向に沿って延在し、前記第１部分を含む中間部分とを含み、
    　前記上方部分の前記第１方向側の末端と前記中間部分の前記第２方向側の末端が連続し、且つ、前記下方部分の前記第１方向側の末端と前記中間部分の前記第３方向側の末端が連続する、請求項１に記載の半導体装置。     The third conductive film is
    An upper portion extending along the first direction and the fourth direction and including the second portion and the fourth portion,
    A lower portion extending along the first direction and the fourth direction and including the third portion and the fifth portion,
    Extending along the second direction and the third direction, including an intermediate portion including the first portion.
    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 third direction side of the intermediate portion. The semiconductor device according to claim 1, wherein the ends of the semiconductor devices are continuous.
  3. 　前記第３導電膜は、
    　　前記第１方向及び前記第４方向に沿って延在し、前記第２部分の一部及び前記第４部分を含む上方部分と、
    　　前記第１方向及び前記第４方向に沿って延在し、前記第３部分の一部及び前記第５部分を含む上方部分と、
    　　前記上方部分の前記第１方向側の末端から前記下方部分の前記第１方向側の末端まで湾曲して延在し、前記第１部分、前記第２部分の残部及び前記第３部分の残部を含む中央部分とを含む、請求項１に記載の半導体装置。     The third conductive film is
    A part of the second part and an upper part including the fourth part extending along the first direction and the fourth direction, and
    An upper portion extending along the first direction and the fourth direction, including a part of the third part and the fifth part, and
    The upper portion is curved and extends from the end on the first direction side to the end on the first direction side of the lower portion, and the remaining portion of the first portion, the second portion, and the third portion is formed. The semiconductor device according to claim 1, further comprising a central portion including.
  4. 　前記第１導電膜は、ゲートとして機能し、
    　前記第２導電膜は、ソース及びドレインの一方として機能し、
    　前記第３電極膜は、ソース及びドレインの他方として機能する、請求項１乃至３のいずれか一項に記載の半導体装置。     The first conductive film functions as a gate and serves as a gate.
    The second conductive film functions as one of a source and a drain, and serves as one of a source and a drain.
    The semiconductor device according to any one of claims 1 to 3, wherein the third electrode film functions as the other of a source and a drain.
  5. 　前記第３導電膜は、分離されている複数のサブ導電膜を含み、
    　前記第１部分乃至前記第５部分の少なくとも一つは、前記複数のサブ導電膜のうちの少なくとも２つのサブ導電膜それぞれの少なくとも一部を含む、請求項１に記載の半導体装置。     The third conductive film includes a plurality of separated sub-conductive films.
    The semiconductor device according to claim 1, wherein at least one of the first portion to the fifth portion includes at least a part of each of at least two sub conductive films among the plurality of sub conductive films.
  6. 　前記第１導電膜は、ゲートとして機能し、
    　前記第２導電膜は、ソース及びドレインの一方として機能し、
    　前記複数のサブ導電膜の少なくとも一つは、ソース及びドレインの他方として機能する、請求項５に記載の半導体装置。     The first conductive film functions as a gate and serves as a gate.
    The second conductive film functions as one of a source and a drain, and serves as one of a source and a drain.
    The semiconductor device according to claim 5, wherein at least one of the plurality of subconductive films functions as the other of the source and the drain.
  7. 　前記第２導電膜及び前記第３導電膜は、同一材料からなる、請求項１乃至６のいずれか一項に記載の半導体装置。 The semiconductor device according to any one of claims 1 to 6, wherein the second conductive film and the third conductive film are made of the same material.
  8. 　前記第２導電膜と略平行に延在する部分を含み、且つ、該部分が前記第４部分と前記第５部分の間に位置する、前記絶縁膜上の第４導電膜をさらに含み、
    　前記第１導電膜は、ゲートとして機能し、
    　前記第２導電膜は、ソース及びドレインの一方として機能し、
    　前記第４導電膜は、ソース及びドレインの他方として機能する、請求項１乃至３及び５のいずれか一項に記載の半導体装置。     Further including a fourth conductive film on the insulating film, which includes a portion extending substantially parallel to the second conductive film, and the portion is located between the fourth portion and the fifth portion.
    The first conductive film functions as a gate and serves as a gate.
    The second conductive film functions as one of a source and a drain, and serves as one of a source and a drain.
    The semiconductor device according to any one of claims 1 to 3 and 5, wherein the fourth conductive film functions as the other of a source and a drain.
  9. 　前記第２導電膜、前記第３導電膜及び前記第４導電膜は、同一材料からなる、請求項８に記載の半導体装置。 The semiconductor device according to claim 8, wherein the second conductive film, the third conductive film, and the fourth conductive film are made of the same material.
  10. 　前記絶縁膜は、フッ素系樹脂を含む、請求項１乃至９のいずれか一項に記載の半導体装置。 The semiconductor device according to any one of claims 1 to 9, wherein the insulating film contains a fluororesin.
  11. 　前記絶縁膜は、パーフルオロ（３ブテニルビニルエーテル）重合体を含む、請求項１乃至９のいずれか一項に記載の半導体装置。 The semiconductor device according to any one of claims 1 to 9, wherein the insulating film contains a perfluoro (3 butenyl vinyl ether) polymer.
  12. 　前記有機半導体膜は、高分子有機半導体材料又は低分子有機半導体材料を含む、請求項１乃至１１のいずれか一項に記載の半導体装置。 The semiconductor device according to any one of claims 1 to 11, wherein the organic semiconductor film includes a high molecular weight organic semiconductor material or a low molecular weight organic semiconductor material.
  13. 　前記低分子有機半導体材料は、アセン骨格又はヘテロアセン骨格を有する化合物である、請求項１２に記載の半導体装置。 The semiconductor device according to claim 12, wherein the small molecule organic semiconductor material is a compound having an acene skeleton or a heteroacene skeleton.
  14. 　前記第１導電膜下の下地膜と、
    　前記下地膜下の基体とをさらに含む、請求項１乃至１３のいずれか一項に記載の半導体装置。     The base film under the first conductive film and
    The semiconductor device according to any one of claims 1 to 13, further comprising a substrate under the undercoat.
  15. 　前記下地膜は、フッ素系樹脂を含む、請求項１４に記載の半導体装置。 The semiconductor device according to claim 14, wherein the base film contains a fluororesin.
  16. 　前記下地膜は、パーフルオロ（３ブテニルビニルエーテル）重合体を含む、請求項１４に記載の半導体装置。 The semiconductor device according to claim 14, wherein the base film contains a perfluoro (3-butenyl vinyl ether) polymer.
  17. 　前記基体は、フレキシブルである、請求項１４乃至１６のいずれか一項に記載の半導体装置。 The semiconductor device according to any one of claims 14 to 16, wherein the substrate is flexible.
  18. 　第１導電膜を製膜する工程と、
    　前記第１導電膜上に絶縁膜を製膜する工程と、
    　前記絶縁膜の第１領域及び第２領域に対して紫外線を照射する工程と、
    　前記第１領域及び前記第２領域に第２導電膜及び第３導電膜をそれぞれ製膜する工程と、
    　前記絶縁膜、前記第２導電膜及び前記第３導電膜上に有機半導体膜を製膜する工程とを含み、
    　前記第１領域は、第１方向に沿って延在し、
    　前記第２領域は、
    　　前記第１領域から見て、前記第１方向に位置する第１部分と、
    　　前記第１領域と前記第１部分の間の領域から見て、前記第１方向と直交する第２方向に位置する第２部分及び前記第２方向の反対方向である第３方向に位置する第３部分と、
    　　前記第２部分から見て、前記第１方向の反対方向である第４方向に位置する第４部分と、
    　　前記第３部分から見て、前記第４方向に位置する第５部分とを含み、
    　前記第１部分、前記第２部分の少なくとも一部及び前記第３部分の少なくとも一部は、連続して延在し、
    　前記有機半導体膜を構成する材料を溶質として含む溶液の主成分となる溶媒の前記ゲート絶縁膜に対する接触角は、前記溶媒の前記第２導電膜及び前記第３導電膜のそれぞれに対する接触角よりも大きく、
    　前記有機半導体膜を製膜する工程は、前記溶液を前記第４方向に沿って塗布する工程を含む、半導体装置の製造方法。     The process of forming the first conductive film and
    The step of forming an insulating film on the first conductive film and
    The step of irradiating the first region and the second region of the insulating film with ultraviolet rays,
    A step of forming a second conductive film and a third conductive film in the first region and the second region, respectively.
    A step of forming an organic semiconductor film on the insulating film, the second conductive film, and the third conductive film is included.
    The first region extends along the first direction and extends.
    The second region is
    The first portion located in the first direction when viewed from the first region, and
    A second portion located in the second direction orthogonal to the first direction and a third direction located in the third direction opposite to the second direction when viewed from the region between the first region and the first portion. 3 parts and
    A fourth portion located in the fourth direction, which is the opposite direction of the first direction when viewed from the second portion,
    Includes a fifth portion located in the fourth direction as viewed from the third portion.
    The first part, at least a part of the second part, and at least a part of the third part are continuously extending.
    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 larger than the contact angle of the solvent with respect to each of the second conductive film and the third conductive film. big,
    A method for manufacturing a semiconductor device, wherein the step of forming the organic semiconductor film includes a step of applying the solution along the fourth direction.
  19. 　第１導電膜を製膜する工程と、
    　前記第１導電膜上に絶縁膜を製膜する工程と、
    　前記絶縁膜の第１領域、第２領域及び第３領域に対して紫外線を照射する工程と、
    　前記第１領域、前記第２領域及び前記第３領域に第２導電膜、第３導電膜及び第４導電膜をそれぞれ製膜する工程と、
    　前記絶縁膜、前記第２導電膜、前記第３導電膜及び前記第４導電膜上に有機半導体膜を製膜する工程とを含み、
    　前記第１領域及び前記第３領域は、第１方向に沿って略平行に延在し、
    　前記第２領域は、
    　　前記第１領域及び前記第３領域から見て、前記第１方向に位置する第１部分と、
    　　前記第１領域及び前記第３領域と前記第１部分の間の領域から見て、前記第１方向と直交する第２方向に位置する第２部分及び前記第２方向の反対方向である第３方向に位置する第３部分と、
    　　前記第２部分から見て、前記第１方向の反対方向である第４方向に位置する第４部分と、
    　　前記第３部分から見て、前記第４方向に位置する第５部分とを含み、
    　前記第１部分、前記第２部分の少なくとも一部及び前記第３部分の少なくとも一部は、連続して延在し、
    　前記有機半導体膜を構成する材料を溶質として含む溶液の主成分となる溶媒の前記ゲート絶縁膜に対する接触角は、前記溶媒の前記第２導電膜、前記第３導電膜及び前記第４導電膜のそれぞれに対する接触角よりも大きく、
    　前記有機半導体膜を製膜する工程は、前記溶液を前記第４方向に沿って塗布する工程を含む、半導体装置の製造方法。     The process of forming the first conductive film and
    The step of forming an insulating film on the first conductive film and
    A step of irradiating the first region, the second region, and the third region of the insulating film with ultraviolet rays, and
    A step of forming a second conductive film, a third conductive film, and a fourth conductive film in the first region, the second region, and the third region, respectively.
    A step of forming an organic semiconductor film on the insulating film, the second conductive film, the third conductive film, and the fourth conductive film is included.
    The first region and the third region extend substantially in parallel along the first direction.
    The second region is
    The first portion located in the first direction when viewed from the first region and the third region, and
    The second portion located in the second direction orthogonal to the first direction and the third direction opposite to the second direction when viewed from the first region and the region between the third region and the first portion. The third part located in the direction and
    A fourth portion located in the fourth direction, which is the opposite direction of the first direction when viewed from the second portion,
    Includes a fifth portion located in the fourth direction as viewed from the third portion.
    The first part, at least a part of the second part, and at least a part of the third part are continuously extending.
    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 the contact angle of the solvent with respect to the second conductive film, the third conductive film and the fourth conductive film. Greater than the contact angle for each
    A method for manufacturing a semiconductor device, wherein the step of forming the organic semiconductor film includes a step of applying the solution along the fourth direction.
  20. 　前記塗布する工程は、
    　　前記溶液を前記絶縁膜上に滴下する工程と、
    　　塗装部材によって前記溶液を前記第４方向に沿って掃引する工程とをさらに含む、請求項１８又は１９に記載の半導体装置の製造方法。     The coating step is
    The step of dropping the solution onto the insulating film and
    The method for manufacturing a semiconductor device according to claim 18 or 19, further comprising a step of sweeping the solution along the fourth direction by a coating member.
  21. 　前記有機半導体膜を製膜する工程の前に、前記溶媒に対する撥液性を有するように前記塗装部材の表面を撥液加工する工程をさらに含む、請求項２０に記載の半導体装置の製造方法。 The method for manufacturing a semiconductor device according to claim 20, further comprising a step of liquid-repellent processing the surface of the coating member so as to have liquid-repellent property against the solvent before the step of forming the organic semiconductor film.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006060079A (en) * 2004-08-20 2006-03-02 Ricoh Co Ltd Patterning method of semiconductor layer, electronic element, electronic element array, display
JP2007300116A (en) * 2006-04-28 2007-11-15 Samsung Electronics Co Ltd Display, and manufacturing method thereof
JP2009141203A (en) * 2007-12-07 2009-06-25 Ricoh Co Ltd Organic transistor, organic transistor array, and display apparatus
JP2009239033A (en) * 2008-03-27 2009-10-15 Toppan Printing Co Ltd Method of manufacturing organic thin-film transistor and/or organic thin-film transistor array, organic thin-film transistor, and organic thin-film transistor array
JP2013157525A (en) * 2012-01-31 2013-08-15 Citizen Holdings Co Ltd Organic transistor
US20130328049A1 (en) * 2012-06-11 2013-12-12 Samsung Display Co., Ltd. Thin-film transistor substrate and method of manufacturing the same
JP2019153653A (en) * 2018-03-02 2019-09-12 三菱ケミカル株式会社 Organic semiconductor device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006060079A (en) * 2004-08-20 2006-03-02 Ricoh Co Ltd Patterning method of semiconductor layer, electronic element, electronic element array, display
JP2007300116A (en) * 2006-04-28 2007-11-15 Samsung Electronics Co Ltd Display, and manufacturing method thereof
JP2009141203A (en) * 2007-12-07 2009-06-25 Ricoh Co Ltd Organic transistor, organic transistor array, and display apparatus
JP2009239033A (en) * 2008-03-27 2009-10-15 Toppan Printing Co Ltd Method of manufacturing organic thin-film transistor and/or organic thin-film transistor array, organic thin-film transistor, and organic thin-film transistor array
JP2013157525A (en) * 2012-01-31 2013-08-15 Citizen Holdings Co Ltd Organic transistor
US20130328049A1 (en) * 2012-06-11 2013-12-12 Samsung Display Co., Ltd. Thin-film transistor substrate and method of manufacturing the same
JP2019153653A (en) * 2018-03-02 2019-09-12 三菱ケミカル株式会社 Organic semiconductor device

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