JP5737505B2 - Method for manufacturing organic semiconductor element - Google Patents

Description

  The present invention relates to a method for manufacturing an organic semiconductor element.

  Conventionally, various methods have been proposed as a method for manufacturing an organic semiconductor element.

  In particular, as a method for patterning an organic semiconductor, a method for patterning an organic semiconductor by forming a pattern having different surface wettability with respect to a liquid has been proposed.

  For example, a transparent conductive film is formed in a pattern on a substrate, and an insulating film is formed in the opening of the transparent conductive film using a material whose surface wettability with respect to the liquid thin film material is changed by light irradiation. And selectively irradiate a portion of the insulating film through a photomask to increase the wettability of the light-irradiated region on the surface of the insulating film to the liquid thin film material, and liquid on the light-irradiated region of the transparent conductive film and the insulating film. A method of forming a thin film in a pattern by applying a thin film material has been proposed (see Patent Document 1). According to this method, by irradiating the insulating film with light, regions having different wettability with respect to the liquid thin film material are formed on the film surface, and by utilizing the difference in wettability of the film surface, the thin film can be efficiently and accurately produced. It can be formed in a pattern.

JP 2004-288469 A

  Regarding the method described in Patent Document 1, the wettability change due to light irradiation has a large effect due to the reaction between the active species of oxygen in the vicinity of the insulating film and the surface of the insulating film, and light in the vacuum ultraviolet region is preferable. In addition, the highest accuracy is obtained when the substrate and the photomask are brought into close contact with light irradiation. However, if the contact is made, the photomask is damaged or contaminated, so that the gap between the substrate and the photomask is as much as possible. It is preferable to make it smaller. However, if there is a space between the substrate and the photomask, when oxygen is irradiated with vacuum ultraviolet rays, the active species of oxygen will also circulate into the area where vacuum ultraviolet rays are not irradiated, resulting in a problem that the pattern is blurred and accuracy is lowered. is there. Therefore, there is a demand for a patterning technique that can form regions with different wettability without employing a photomask and that can form an organic semiconductor with high accuracy and efficiency.

  The present invention has been made in view of the above problems, and can form regions having different wettability without employing a photomask, and can pattern an organic semiconductor with high accuracy and efficiency. It aims at providing the manufacturing method of an organic-semiconductor element.

In order to achieve the above object, the present invention includes a substrate having a liquid repellent portion having liquid repellency with respect to a solution for forming an organic semiconductor layer containing an organic semiconductor material in a solvent, and the substrate formed on the substrate. For an organic semiconductor element having a source electrode and a drain electrode and a shielding layer formed on a part of the liquid repellent portion of the substrate, wherein the source electrode and the drain electrode contain gold or / and platinum. A part of the liquid-repellent part of the substrate is irradiated with ultraviolet rays or oxygen-containing plasma from the side where the source electrode and drain electrode of the substrate for organic semiconductor elements are formed on the substrate. Removing the shielding layer from the base of the organic semiconductor element substrate, the step of forming an organic semiconductor element substrate that is modified into a lyophilic part having lyophilicity with respect to the organic semiconductor layer forming solution, Substrates for organic semiconductor devices The organic semiconductor layer forming solution was applied to provide a method of manufacturing an organic semiconductor device having a step of forming the organic semiconductor layer for forming the organic semiconductor layer in contact with the source electrode and the drain electrode.
In order to achieve the above object, the present invention provides a substrate having a liquid repellent portion having liquid repellency with respect to a solution for forming an organic semiconductor layer containing an organic semiconductor material in a solvent, and formed on the substrate. A source electrode and a drain electrode, and a shielding layer formed on a part of the liquid-repellent portion of the substrate, and a metal having a redox potential of silver or less is present on both or one of the source electrode and the drain electrode. Ultraviolet light or oxygen-containing plasma is applied to the organic semiconductor element substrate from the side where the source electrode and the drain electrode of the organic semiconductor element substrate are formed on the organic semiconductor element substrate substrate in an atmosphere containing oxygen. Forming a substrate for an organic semiconductor element by irradiating the substrate and modifying a part of the liquid-repellent portion of the base body into a lyophilic portion having lyophilicity to the organic semiconductor layer forming solution; And the dray A reduction step of a source electrode and a drain electrode for reducing a metal having an oxidation-reduction potential of silver or less contained in the electrode; and the shielding layer is removed from the base of the organic semiconductor element substrate, and the organic semiconductor element substrate There is provided a method for producing an organic semiconductor element, comprising: applying an organic semiconductor layer forming solution thereon; and forming an organic semiconductor layer to form the organic semiconductor layer in contact with the source electrode and the drain electrode.

  In the present invention, in the step of forming the substrate for an organic semiconductor element, when a part of the liquid-repellent part on the substrate is modified into a lyophilic part, the part where the liquid-repellent property is to be maintained is covered with a shielding layer, Since it is protected, the organic semiconductor can be efficiently patterned with high accuracy.

It is process drawing which shows an example (when a source electrode and a drain electrode are gold | metal | money or platinum with a top gate / bottom contact type structure) of the manufacturing method of the organic-semiconductor element of this invention. Process drawing which shows an example of the manufacturing method of the organic-semiconductor element of this invention (When a metal whose oxidation-reduction potential is silver or less is contained in both or one of the source electrode and the drain electrode in the top gate / bottom contact type structure) It is. It is process drawing which shows an example (when a source electrode and a drain electrode are gold | metal | money or platinum with a bottom gate / bottom contact type structure) of the manufacturing method of the organic-semiconductor element of this invention. Process drawing which shows an example of the manufacturing method of the organic-semiconductor element of this invention (When the metal whose oxidation-reduction potential is silver or less is contained in both or one of the source electrode and the drain electrode in the bottom gate / bottom contact type structure) It is.

  Hereinafter, the manufacturing method of the organic-semiconductor element of this invention is demonstrated in detail.

  The method for producing an organic semiconductor element of the present invention comprises at least a step for forming an organic semiconductor element substrate and a step for forming an organic semiconductor layer when the source electrode and the drain electrode contain gold or / and platinum. . In addition, when both or one of the source electrode and the drain electrode contains a metal having an oxidation-reduction potential of silver or lower, the organic semiconductor element substrate forming step, the source and drain electrode reducing step, and the organic semiconductor layer It is comprised at least by a formation process.

  In the case where the source electrode and the drain electrode contain gold or / and platinum, the organic semiconductor element substrate forming step is liquid repellent with respect to the organic semiconductor layer forming solution containing the organic semiconductor material in the solvent. A substrate having a liquid-repellent portion, a source electrode and a drain electrode formed on the substrate, and a shielding layer formed on a part of the liquid-repellent portion of the substrate, the source electrode and the The drain electrode is formed on an organic semiconductor element substrate containing gold or / and platinum, and ultraviolet or oxygen-containing plasma is applied to the organic semiconductor element from the side where the source electrode and the drain electrode of the organic semiconductor element substrate are formed. The element substrate is irradiated to denature a part of the lyophobic portion of the base body into a lyophilic portion having lyophilicity with respect to the organic semiconductor layer forming solution. The organic semiconductor layer forming step includes removing the shielding layer from the base of the organic semiconductor element substrate, applying the organic semiconductor layer forming solution on the organic semiconductor element substrate, The organic semiconductor layer in contact with the drain electrode is formed.

  In the case where a metal having an oxidation-reduction potential of silver or less is contained in one or both of the source electrode and the drain electrode, the organic semiconductor element substrate forming step is for forming an organic semiconductor layer containing an organic semiconductor material in a solvent. A substrate having a liquid repellent portion having liquid repellency to the solution; a source electrode and a drain electrode formed on the substrate; and a shielding layer formed on a part of the liquid repellent portion of the substrate. A source of the organic semiconductor element substrate in an atmosphere containing oxygen on an organic semiconductor element substrate in which a metal having a redox potential of silver or less is contained in both or one of the source electrode and the drain electrode. The substrate for organic semiconductor element is irradiated with ultraviolet rays or oxygen-containing plasma from the side on which the electrode and drain electrode are formed, and a part of the liquid repellent portion of the substrate is applied to the organic semiconductor layer forming solution. It is intended to modify the lyophilic portion is lyophilic. Moreover, the reduction | restoration process of a source electrode and a drain electrode reduces the metal whose oxidation-reduction potential contained in the said source electrode and the said drain electrode is silver or less. The organic semiconductor layer forming step includes removing the shielding layer from the base of the organic semiconductor element substrate, applying the organic semiconductor layer forming solution on the organic semiconductor element substrate, The organic semiconductor layer in contact with the drain electrode is formed.

The manufacturing method of the organic semiconductor element of this invention is demonstrated referring drawings.
1A to 1I are process diagrams showing an example of a method for manufacturing an organic semiconductor element in the case where the source electrode and the drain electrode are gold or platinum in the top gate / bottom contact type structure of the present invention.

  First, a substrate having a liquid repellent portion having liquid repellency with respect to a solution for forming an organic semiconductor layer in which an organic semiconductor material is dissolved in a solvent is prepared (FIG. 1 (1a)). Next, a source electrode and a drain electrode containing gold and / or platinum are formed on the substrate (FIG. 1 (1b)). Next, a shielding layer is formed on a part of the liquid repellent portion of the substrate (FIG. 1 (1c)). Next, by irradiating the organic semiconductor element substrate with ultraviolet rays or oxygen-containing plasma (FIG. 1 (1d)), a part of the lyophobic part of the substrate is lyophilic with respect to the organic semiconductor layer forming solution. Denatured into the lyophilic part (FIG. 1 (1e)). As described above, a substrate for an organic semiconductor element including a base body having a lyophilic portion, a shielding layer, a source electrode, and a drain electrode is manufactured. Subsequently, the shielding layer is removed from the liquid repellent portion of the organic semiconductor element substrate (FIG. 1 (1f)). Next, an organic semiconductor layer forming solution is applied on the organic semiconductor element substrate to form an organic semiconductor layer in contact with the source electrode and the drain electrode (FIG. 1 (1g)). Subsequently, a gate insulating layer material is formed on the organic semiconductor element substrate on the side where the source electrode and the drain electrode of the organic semiconductor element substrate are formed (FIG. 1 (1h)). Next, a gate electrode is formed on the gate insulating layer (FIG. 1 (1i)).

  FIGS. 2 (2a) to (2k) are organic semiconductor devices in the case where a metal having an oxidation-reduction potential of silver or less is contained in both or one of the source electrode and the drain electrode in the top gate / bottom contact type structure of the present invention. It is process drawing which shows an example of this manufacturing method.

  First, a substrate having a liquid repellent portion having liquid repellency with respect to a solution for forming an organic semiconductor layer in which an organic semiconductor material is dissolved in a solvent is prepared (FIG. 2 (2a)). Next, a source electrode and a drain electrode containing a metal having a redox potential of silver or less on both or one side are formed on the substrate (FIG. 2 (2b)). Next, a shielding layer is formed on a part of the liquid repellent portion of the substrate (FIG. 2 (2c)). Next, by irradiating the organic semiconductor element substrate with ultraviolet rays or oxygen-containing plasma, a part of the lyophobic portion of the substrate is denatured into a lyophilic portion having lyophilicity with respect to the organic semiconductor layer forming solution ( FIG. 2 (2d) and FIG. 2 (2e)). As described above, a substrate for an organic semiconductor element including a base body having a lyophilic portion, a shielding layer, a source electrode, and a drain electrode is manufactured. Subsequently, the source electrode and the drain electrode are reduced (FIG. 2 (2f), FIG. 2 (2g)). Subsequently, the shielding layer is removed from the liquid repellent portion of the organic semiconductor element substrate (FIG. 2 (2h)). Next, an organic semiconductor layer forming solution is applied on the organic semiconductor element substrate to form an organic semiconductor layer in contact with the source electrode and the drain electrode (FIG. 2 (2i)). Subsequently, a gate insulating layer is formed on the organic semiconductor element substrate on the side where the source electrode and the drain electrode of the organic semiconductor element substrate are formed (FIG. 2 (2j)). Next, a gate electrode is formed on the gate insulating layer (FIG. 2 (2k)).

  FIG. 3 is a process diagram showing an example of a method of manufacturing an organic semiconductor device in the case where the source electrode and the drain electrode are gold or platinum in the bottom gate / bottom contact type structure of the present invention. 1 except that a gate electrode is included.

  FIG. 4 shows an example of a method for manufacturing an organic semiconductor element in the case where a metal having an oxidation-reduction potential of silver or less is contained in one or both of the source electrode and the drain electrode in the bottom gate gate / bottom contact type structure of the present invention. 2 is the same as FIG. 2 except that the structure of the base includes a gate insulating layer and a gate electrode.

According to the present invention, in the step of forming the substrate for an organic semiconductor element, when a part of the liquid-repellent part on the substrate is modified into the lyophilic part, the part where the liquid-repellent property is to be maintained is covered with the shielding layer. Therefore, the organic semiconductor can be patterned with high accuracy and efficiency.
A. Hereinafter, each process in the manufacturing method of the organic-semiconductor element of 1st embodiment of this invention is demonstrated.
1A. Step of forming substrate for organic semiconductor element The step of forming the substrate for organic semiconductor element includes a substrate having a liquid repellent portion having liquid repellency with respect to an organic semiconductor layer forming solution containing an organic semiconductor material in a solvent; A source electrode and a drain electrode formed on the substrate, and a shielding layer formed on a part of the liquid repellent portion of the substrate, wherein the source electrode and the drain electrode contain gold or / and platinum. The organic semiconductor element substrate is irradiated with ultraviolet light or oxygen-containing plasma from the side on which the source electrode and drain electrode of the organic semiconductor element substrate are formed on the organic semiconductor element substrate. A part of the lyophobic part is modified into a lyophilic part having a lyophilic property to the organic semiconductor layer forming solution.

1A-1. The substrate for organic semiconductor elements The substrate for organic semiconductor elements is comprised at least by the base | substrate which has a lyophilic part, the shielding layer, the source electrode, and the drain electrode.

1A-1-1. Solution for forming an organic semiconductor material layer The solution for forming an organic semiconductor layer contains an organic semiconductor material in a solvent. The inclusion of the organic semiconductor material in the solvent may be a state where all of the organic semiconductor material is dissolved in the solvent, a state where a part of the organic semiconductor material is not dissolved in the solvent, or may be dispersed. The semiconductor material may be dispersed in a solvent. Examples of the organic semiconductor material of the organic semiconductor layer forming solution include polyacetylene derivatives, polythiophene derivatives having a thiophene ring, poly (3-alkylthiophene) derivatives, poly (3,4-ethylenedioxythiophene) derivatives, and polythienylene vinylene derivatives. And conjugated polymer compounds such as a polyphenylene derivative having a benzene ring, a polyphenylene vinylene derivative, a polypyridine derivative having a nitrogen atom, a polypyrrole derivative, a polyaniline derivative, and a polyquinoline derivative. A polythiophene derivative suitable for coating formation is preferable.

  The solvent of the organic semiconductor layer forming solution is not particularly limited as long as the organic semiconductor contains, but is preferably an organic solvent having high solubility of the organic semiconductor.

  The method for producing the organic semiconductor layer forming solution is not particularly limited as long as it is a general solution producing method such as a method of adding an organic semiconductor material to a solvent or a method of adding a solvent to an organic semiconductor material.

1A-1-2. Substrate The substrate has a liquid repellent portion that has liquid repellency with respect to a solution for forming an organic semiconductor layer containing an organic semiconductor material in a solvent.

  As the substrate, resin, plastic film, glass, quartz, aluminum oxide, sapphire, silicon nitride, silicon carbide and other ceramic substrates, silicon, germanium, gallium arsenide, gallium phosphide, gallium nitrogen and other semiconductor substrates, paper, nonwoven fabric, etc. Can be used. Among them, the liquid repellent part is preferably made of a resin or a plastic film. Examples of the resin include polyester resin, polycarbonate resin, cellulose resin, gelatin, acrylic resin, polyurethane resin, polyethylene resin, polypropylene resin, polystyrene resin, phenoxy resin, norbornene resin, epoxy resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride. Resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially hydrolyzed vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol Copolymers, polyvinyl alcohol, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymers, vinyl polymers such as ethylene-vinyl acetate copolymers, polyamide resins, ethylene-butadiene resins, butadiene-acrylonites Rubber-based resins such as Le resins, alkyd resins, phenol resins, urea resins, silicone resins, fluorine-based resins. In addition, as a plastic film, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), Examples thereof include films made of cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like. Furthermore, a thin film made of a metal such as stainless steel or aluminum having a thickness that can be bent can also be used. Moreover, the base | substrate may have a base material on the opposite side to the surface which forms the organic-semiconductor element of a base | substrate. As the base material, in addition to the same material as the liquid repellent part, a thin film made of a metal such as stainless steel or aluminum having a thickness capable of bending can be used. Preferably, a plastic film that can reduce the weight as compared with the case where glass is used for the base material, can improve portability, and can improve resistance to impact is preferable. In addition, when a plastic film is used as a base material, it is possible to incorporate or integrate a field effect transistor into a display device or electronic device having a curved shape. Further, in the case of a bottom gate type structure, the substrate may also serve as a gate insulating layer. Furthermore, you may provide a gate electrode and a base material on the opposite side to the surface which forms the organic-semiconductor element of a gate insulating layer.

1A-1-3. Liquid repellent part The liquid repellent part is liquid repellent with respect to a solution for forming an organic semiconductor layer containing an organic semiconductor material in a solvent. As the liquid repellency, the contact angle of the solvent of the organic semiconductor layer forming solution at 25 ° C. on the surface of the liquid repellent part is formed on the surface of the liquid repellent part in the step of forming the substrate for the organic semiconductor element. It is necessary that the contact angle of the solvent of the organic semiconductor layer forming solution at 25 ° C. on the surface of the lyophilic portion having lyophilicity with the solution for use is larger. This is because it is necessary to fix the organic semiconductor layer forming solution only on the lyophilic portion in order to pattern the organic semiconductor layer in the step of forming the organic semiconductor layer. Preferably, the contact angle of the solvent of the solution for forming an organic semiconductor layer at 25 ° C. on the surface of the liquid repellent part is preferably 80 ° or more, and particularly preferably 100 ° or more.

  The contact angle can be measured, for example, by dropping 1 microliter of liquid onto the substrate, observing the shape of the dropped droplet from the side, and measuring the angle formed by the droplet and the substrate. it can. Such a measurement can be performed by, for example, a contact angle measuring device manufactured by Imoto Seisakusho.

  The form of the liquid repellent part is not particularly limited as long as the liquid repellent part is provided on the side of the base on which the organic semiconductor layer is formed. For example, the whole substrate may be a liquid repellent material, or a liquid repellent material may be formed on a part of the surface of the substrate on the side where the organic semiconductor layer is formed. .

  As a method for preparing a substrate having a liquid repellent portion, a material having liquid repellency may be prepared when the entire substrate is in a form of a material having liquid repellency. In the case where a material having liquid repellency is formed on a part of the surface of the base on which the organic semiconductor layer is formed, the material having liquid repellency may be formed on the substrate. The method for forming a liquid repellent material on the substrate is not particularly limited as long as the liquid repellent material can be formed on the substrate.

  As the material for the liquid repellent portion, the above-mentioned base material can be used. Preferably, acrylic resin, silicone resin, and fluorine-based resin are preferable because they have high liquid repellency and are easily modified from liquid repellency to lyophilicity.

1A-1-4. Shielding layer The shielding layer is provided in a region on the base where it is desired to maintain liquid repellency when the liquid repellent part is modified into a lyophilic part. The position of the shielding layer is adjacent to the source electrode and the drain electrode on the substrate. The shielding layer is not particularly limited as long as it is stable to a physical method or a chemical method to be described later when the liquid repellent part is modified into a lyophilic part, but it is preferably handled. Photoresist is good because it is easy to remove.

  When a metal is used for the shielding layer, the material is not particularly limited, but metal particles or metal oxides containing one or more of Cu, Ag, Al, Zn, W, Mo, V, Cr, Ni, Mn, Co, etc. And particles. As a method for forming a metal on a substrate, metal is deposited by sputtering or vapor deposition, and patterning is performed by etching or the like.

  When a resin is used for the shielding layer, the same material as that of the above-described substrate can be used. Preferably, thermosetting resin such as phenol resin, epoxy resin, urea resin, alkyd resin is preferable because of high durability. As a method for forming the resin on the substrate, the same method as that for the liquid repellent portion can be used.

  When a photoresist is used for the shielding layer, either a positive photoresist or a negative photoresist may be used. Among these, a positive photoresist is preferable in consideration of the ease of removing the photoresist in the step of removing the shielding layer described later. As the photoresist, a general one can be used. Among these, it is preferable that the photoresist contains a surfactant containing a fluorine group. With such a photoresist, the surface tension of the photoresist can be effectively reduced. Therefore, even if the liquid repellency of the liquid repellent part is high, the photoresist is satisfactorily coated on the liquid repellent part. Because it can. The surfactant containing a fluorine group is not particularly limited as long as it is soluble in a photoresist, and both a high molecular weight type and a low molecular weight type can be used. Agents can be used.

  Further, the photoresist preferably has a contact angle of 15 ° or less of the photoresist on the surface of the liquid repellent part, and more preferably 10 ° or less. This is because if the contact angle is in the above range, a photoresist can be satisfactorily applied on the liquid repellent portion.

  The method for forming a photoresist on a substrate is not particularly limited as long as it is a method capable of forming a photoresist on a substrate. Usually, a photoresist is coated on a substrate and patterned. A method of forming a photoresist is used.

  The method for applying the photoresist is not particularly limited as long as it can be applied on the liquid repellent portion. For example, spin coating, casting, dip coating, bar coating, blade coating, roll coating, gravure A coat, spray coat, flexographic printing or the like is used.

  The film thickness of the photoresist is not particularly limited as long as it can protect the liquid repellent part in the fourth step described later.

  For patterning the photoresist, a method of patterning the photoresist and developing it is usually used. As a method for pattern exposure of the photoresist, for example, a general method such as a method of exposing through a photomask or a laser drawing method can be used. As a method for developing the photoresist, for example, a method using a developer can be applied. As the developer, a commonly used organic alkaline developer can be used. In addition, an inorganic alkaline developer or an aqueous solution can also be used as the developer. It is preferable to wash with water after developing the photoresist. The photoresist pattern is not particularly limited as long as it can form a desired lyophilic portion, and is appropriately selected.

1A-1-5. Lipophilic part The lyophilic part is lyophilic with respect to the organic semiconductor layer forming solution. As the lyophilic property, the contact angle of the solvent of the organic semiconductor layer forming solution at 25 ° C. on the surface of the lyophilic portion is the solvent of the organic semiconductor layer forming solution at 25 ° C. of the surface of the liquid repellent portion before the third step. It is necessary to be larger than the contact angle. This is because it is necessary to fix the organic semiconductor layer forming solution only on the lyophilic portion in order to pattern the organic semiconductor layer in the step of forming the organic semiconductor layer. Preferably, the contact angle of the solvent of the organic semiconductor layer forming solution at 25 ° C. on the surface of the lyophilic part is preferably 30 ° or less, more preferably 10 ° or less, and 5 ° or less. Is more preferable. Also, the contact angle of the solvent of the organic semiconductor layer forming solution at 25 ° C. on the surface of the lyophilic part, and the contact angle of the solvent of the machine semiconductor layer forming solution at 25 ° C. on the surface of the liquid repellent part before the third step The difference is preferably 50 ° or more, more preferably 70 ° or more, still more preferably 80 ° or more, and particularly preferably 90 ° or more. When the difference between the contact angle of the lyophilic part and the contact angle of the lyophobic part is in the above-described range, the organic semiconductor layer forming solution is more highly selective on the lyophilic part when manufacturing an organic semiconductor element. This is because the organic semiconductor layer can be formed with high accuracy.

    The contact angle can be measured, for example, by dropping 1 microliter of liquid onto the substrate, observing the shape of the dropped droplet from the side, and measuring the angle formed by the droplet and the substrate. it can. Such a measurement can be performed by, for example, a contact angle measuring device manufactured by Imoto Seisakusho.

  As a method for making a part of the lyophobic portion of the substrate lyophilic with respect to the organic semiconductor layer forming solution, a method of irradiating ultraviolet rays and / or oxygen-containing plasma is used. The method of irradiating with ultraviolet rays and / or oxygen-containing plasma is suitable as a method for improving wettability because the surface energy of the liquid repellent part can be particularly increased. Irradiation with ultraviolet rays and / or oxygen-containing plasma increases the surface roughness of the liquid repellent part and / or modifies the functional group on the surface of the liquid repellent part to modify the polar group so that the liquid repellent part is modified into a lyophilic part. can do. Irradiation with ultraviolet rays in an atmosphere of oxygen, such as in a vacuum filled with oxygen in the atmosphere, ozone is generated and polar groups such as hydroxyl groups can be modified to functional groups on the surface of the liquid repellent part. Can be denatured into a lyophilic part. The ultraviolet light is not particularly limited as long as it has a wavelength of 1 nm to 380 nm, such as near ultraviolet light, vacuum ultraviolet light, and extreme ultraviolet light. Among these, vacuum ultraviolet rays are preferable. This is because vacuum ultraviolet rays have high energy, can generate active species of oxygen more effectively, and can efficiently denature the surface of the liquid repellent part into a lyophilic part in a short time. Further, the wavelength of the vacuum ultraviolet ray may be any wavelength as long as the surface of the liquid repellent part can be modified into a lyophilic part, and is appropriately selected according to the type of material of the liquid repellent part. Usually, it is preferably within a range of 100 nm to 250 nm, and more preferably within a range of 150 nm to 200 nm. This is because if the wavelength is longer than the above range, the generation efficiency of oxygen radicals is lowered, and the sensitivity may be lowered depending on the type of material of the liquid repellent part. Further, if the wavelength is shorter than the above range, stable vacuum ultraviolet irradiation may be difficult. Examples of the light source that can be used for irradiation with vacuum ultraviolet rays include an excimer lamp, a low-pressure mercury lamp, and various other light sources. The irradiation amount of vacuum ultraviolet rays is appropriately adjusted according to the type of material of the liquid repellent part.

1A-1-6. Source electrode and drain electrode As a material of the source electrode and the drain electrode, gold or / and platinum are used. The advantage of using gold or / and platinum is that gold and platinum are not oxidized when irradiated with ultraviolet light or oxygen-containing plasma. Since gold and platinum are not oxidized when irradiated with ultraviolet rays or oxygen-containing plasma, it can be prevented that the organic semiconductor element does not function.

  The source electrode and drain electrode are formed by plasma CVD method, thermal CVD method, laser CVD method and other CVD methods, vacuum deposition method, sputtering method, ion plating method and other PVD methods, electrolytic plating method, immersion plating method, There is no particular limitation as long as it is formed on the substrate by an electroless plating method, a sol-gel method, an organometallic decomposition (MOD) method, or the like. Further, the source electrode and the drain electrode may be patterned by a photolithography method or the like. Further, although the source electrode and the drain electrode are separated from each other, the distance to be separated is not particularly limited. Further, the source electrode and the drain electrode may be in contact with the shielding layer in a cross section when the base is viewed from the direction of forming the semiconductor element, but from the shielding layer in a cross section when the base is viewed from the direction perpendicular to the direction of forming the semiconductor element. Although it forms apart, the distance to separate is not specifically limited.

The source electrode and the drain electrode may be formed before the shielding layer is formed or after the shielding layer is formed. Preferably, it is preferable that the shielding layer is not damaged when the source electrode and the drain electrode are formed. Therefore, the source electrode and the drain electrode are formed before the shielding layer is formed.
2A. Step of forming organic semiconductor layer In the step of forming organic semiconductor layer of the present invention, the shielding layer is removed from the base of the substrate for organic semiconductor element, the organic semiconductor layer forming solution is applied on the substrate for organic semiconductor element, and the source An organic semiconductor layer in contact with the electrode and the drain electrode is formed.

2A-1. Removal of shielding layer The method of removing the shielding layer is not particularly limited because it depends on the material on which the shielding layer is formed. For example, if a photoresist pattern is used, it may be removed with a stripping solution. If a metal film pattern is used, it may be removed with an etchant.

2A-2. Method for applying organic semiconductor layer forming solution The method for applying the organic semiconductor layer forming solution on the lyophilic portion is not particularly limited as long as the organic semiconductor layer forming solution can be applied. Examples thereof include dip coating, bar coating, LB, roll coating, spray coating, die coating, bead coating, spin coating, ink jet, dispenser, cast, blade coating, flexographic printing, and gravure printing.

  In the organic semiconductor layer patterning method of the present invention, the organic semiconductor layer forming solution that is fixed only on the lyophilic portion is applied to the substrate divided into the lyophilic portion and the lyophobic portion. Can do.

  In the present invention, it is preferable to form the organic semiconductor layer after removing the light shielding layer. This is because if the organic semiconductor layer is formed before removing the light shielding layer, the organic semiconductor layer forming material adheres to the shielding layer, but the shielding layer is removed so that the organic semiconductor layer forming material attached to the shielding layer is reused. Can not do it. On the other hand, when the organic semiconductor layer is formed after removing the light shielding layer as in the present invention, the organic semiconductor layer forming material can be recovered and reused because it is repelled except in the lyophilic portion. . As described above, the organic semiconductor layer forming material can be efficiently used by reducing the organic semiconductor layer forming material attached to the light shielding layer.

2A-3. Gate Insulating Layer and Gate Electrode The manufacturing method of the present invention includes a step for forming a substrate for an organic semiconductor element and a step for forming an organic semiconductor layer, and may include the following steps for forming a gate insulating layer and a gate electrode.

  In the method for manufacturing an organic semiconductor element having a top gate / bottom contact structure and a top gate / top contact structure, there may be a case where a gate insulating layer and a gate electrode are formed after the organic semiconductor layer is formed. In the step of forming the gate insulating layer and the gate electrode, the gate insulating layer is formed so as to cover at least the organic semiconductor layer between the source electrode and the drain electrode, and the gate electrode is formed on the gate insulating layer. For example, a gate insulating layer material is formed by spin coating on the organic semiconductor element substrate on the side where the source electrode and drain electrode of the organic semiconductor element substrate are formed, exposed through a photomask, and heated and cured. Then, a gate insulating layer is formed. Next, a method of forming a gate electrode by depositing a gate electrode material on a gate insulating layer through a metal mask and patterning by a photolithography method can be mentioned.

  In the manufacturing method of the organic semiconductor device having the bottom gate / bottom contact type structure and the bottom gate / top contact type structure, there may be a case where the gate insulating layer and the gate electrode are formed in the substrate. It is done. For example, a gate electrode material is vapor-deposited on a substrate through a metal mask, and patterned by a photolithography method to form a gate electrode. Next, a gate insulating layer material is formed by spin coating, exposed through a photomask, heated and cured, and a gate insulating layer is formed to form a gate insulating layer and a gate electrode in the substrate. it can.

  The gate insulating layer material is polyester resin, polycarbonate resin, cellulose resin, gelatin, acrylic resin, polyurethane resin, polyethylene resin, polypropylene resin, polystyrene resin, phenoxy resin, norbornene resin, epoxy resin, vinyl chloride-vinyl acetate copolymer, Vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially hydrolyzed vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene- Vinyl alcohol copolymers, polyvinyl alcohol, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymers, vinyl polymers such as ethylene-vinyl acetate copolymers, polyamide resins, ethylene-butadiene resins, butadiene-acrylic Rubber-based resins such as nitrile resins, silicone resins, and fluorine resins. The gate electrode material is not particularly limited as long as it has conductivity, but metal particles or metal oxide particles such as Au, Cu, Ag, ITO and Pt, carbon materials such as graphene and carbon nanotubes, PEDOT / PSS And the like, and the like.

In a method for manufacturing an organic semiconductor element having a bottom gate / bottom contact type structure, a case where a gate insulating layer and a gate electrode are included in the substrate may be considered. When the base includes a gate insulating layer and a gate electrode, the step of forming the gate insulating layer and the gate electrode is to prepare a base material, form the gate electrode on the base material, and repel the liquid so as to cover the gate electrode A gate insulating layer having a property is formed. As the substrate, those described above can be preferably used.
3A. Structure of Organic Semiconductor Element The structure of the organic semiconductor element of the present invention will be described. The organic semiconductor element of the present invention includes a substrate, a source electrode, a drain electrode, an organic semiconductor layer, a gate insulating layer, and a gate electrode. Note that the gate insulating layer and the gate electrode are appropriately arranged depending on the mold. For example, in a top gate / bottom contact type structure and a top gate / top contact type structure, a gate insulating layer and a gate electrode are disposed on the organic semiconductor layer. In the bottom gate / bottom contact type structure and the bottom gate / top contact type structure, a gate insulating layer and a gate electrode are disposed on a part of the substrate.

Since the organic semiconductor element may be broken by an etchant used when forming the gate electrode and the drain electrode, a top gate / bottom contact type structure or a bottom gate / bottom contact type structure is preferable.
B. Hereinafter, each process in the manufacturing method of the organic-semiconductor element of 2nd embodiment of this invention is demonstrated.
1B. Step of forming substrate for organic semiconductor element The step of forming the substrate for organic semiconductor element includes a substrate having a liquid repellent portion having liquid repellency with respect to an organic semiconductor layer forming solution containing an organic semiconductor material in a solvent; A source electrode and a drain electrode formed on the substrate, and a shielding layer formed on a part of the liquid repellent portion of the substrate, and a redox potential is applied to both or one of the source electrode and the drain electrode. On the organic semiconductor element substrate containing a metal below silver, ultraviolet or oxygen-containing plasma is applied from the side where the source electrode and drain electrode of the organic semiconductor element substrate are formed in an atmosphere containing oxygen. The organic semiconductor element substrate is irradiated to denature a part of the lyophobic portion of the substrate into a lyophilic portion having lyophilicity with respect to the organic semiconductor layer forming solution.

1B-1. Organic Semiconductor Device Substrate Organic semiconductor device substrate can be used to organically irradiate ultraviolet or oxygen-containing plasma in an oxygen-containing atmosphere in which one or both of a source electrode and a drain electrode contain a metal having a redox potential of silver or less. Except for irradiating the substrate for semiconductor elements, 1A-1. The configuration is the same as that described in.

1B-1-1. Source electrode and drain electrode Both or one of the source electrode and the drain electrode contains a metal having a redox potential of silver or less. Examples of the metal having a redox potential equal to or lower than silver include silver, copper, bismuth, antimony, lead, tin, nickel, cobalt, cadmium, iron, chromium, zinc, tantalum, and manganese. Among them, silver which has good electrical conductivity and is easily available is preferable. Moreover, the metal whose oxidation-reduction potential is equal to or lower than silver is a concept including not only a single metal but also an alloy. Further, when the alloy contains a single metal having a redox potential larger than silver and contains a single metal having a redox potential of silver or lower, the alloy is included in the concept of containing a metal having a redox potential of silver or lower. . As an alloy contained in a metal having a redox potential equal to or lower than silver, an APC alloy (AgPdCu alloy) is particularly preferable because it has good electrical conductivity. In general, a metal having an oxidation-reduction potential of silver or less is much cheaper than gold and platinum. Therefore, the cost of a member can be reduced by using a metal having an oxidation-reduction potential of silver or less. However, a metal having an oxidation-reduction potential equal to or lower than silver is oxidized by ultraviolet rays or oxygen-containing plasma, so that a reduction process described later is required. Note that the redox potential of silver is 0.799V.
2B. Reduction process of source electrode and drain electrode The reduction process of the source electrode and the drain electrode is to reduce a metal having an oxidation-reduction potential of silver or less contained in the source electrode and the drain electrode.

2B-1. Reduction Method The reduction method is not particularly limited as long as it is a method capable of reducing a metal having a redox potential of silver or less, such as reduction by heating or reduction by a reducing agent.

  In the reduction method by heating, the organic semiconductor element substrate is heated at a temperature at which a metal oxide having a redox potential of silver or lower is decomposed. Reduction by heating can reduce the manufacturing cost because there are few steps.

  The reducing method using a reducing agent is particularly suitable as long as the reducing agent in various states such as gas, liquid and solid is brought into contact with a metal whose oxidation-reduction potential contained in the oxidized source electrode and drain electrode is lower than silver. It is not limited. Preferably, a reduction method in which reduction treatment is performed in a hydrogen plasma atmosphere that facilitates uniform reduction of metal oxides, hydrogen, carbon monoxide, or the like, or hydrogen, carbon monoxide such as nitrogen, helium, argon, etc. A reducing method in which a reducing gas diluted with an inert gas is used and reduction is performed in the reducing gas atmosphere can be suitably used. As the reducing gas, one kind of reducing gas may be used alone, or two or more kinds of gases may be mixed and used.

For the reduction with a reducing agent, various reducing agents such as a simple substance, a hydride, and an oxide can be used. Further, the reducing agent is not particularly limited as long as the redox potential contained in the source electrode and the drain electrode is smaller than that of silver or less. Examples of simple substances include hydrogen, carbon, phosphorus, sodium, magnesium, and metal amalgam. Examples of hydrides include hydrogen iodide, hydrogen sulfide, ammonia and derivatives thereof, hydrogen phosphide, and arsenic hydride. . Examples of the oxide include carbon monoxide, sulfur dioxide, phosphorus trioxide, arsenous acid, phosphorous acid, nitrous acid, and sulfurous acid. Reduction with a reducing agent can effectively reduce an oxide having a high temperature for thermal decomposition.
3B. Step of forming organic semiconductor layer The step of forming the organic semiconductor layer is 2A. Perform in the same way.
4B. Structure of organic semiconductor element The structure of the organic semiconductor element is 3A. Can take the same structure.
5. Applications Examples of the use of the organic semiconductor element produced by the method for producing an organic semiconductor element of the present invention include a liquid crystal display device, an electrophoretic display device, and an organic EL display device.

  The following examples illustrate the present invention in more detail.

  A top gate / bottom contact type organic semiconductor element described below was produced. A glass (thickness: 0.7 mm) made of silicon dioxide is spin-coated with a liquid-repellent acrylic silicone resin (Shin-Etsu Chemical Co., KP-545) and heated in an oven (ESPEC clean oven) at 150 ° C. for 30 minutes. A substrate (thickness: 5 μm) was formed by curing. The contact angle is measured by the θ / 2 method, which is a method for determining the contact angle from the angle of the straight line connecting the left and right end points and the apex of the droplet to the solid surface by dropping 1.2 μl of 25 ° C. trichlorobenzene onto the substrate surface. As a result, the contact angle was 98.0 °.

  Next, Au (40 nm) was formed on the entire surface of the substrate by a vacuum evaporation method (ULVAC vacuum evaporation apparatus) to obtain an Au film as a golden film. A positive photoresist (AZ-5206, manufactured by AZ Electronic Materials) is formed on the Au film by spin coating, exposed through a photomask, and then an aqueous tetramethylammonium hydroxide solution (concentration: 2.). The photoresist was patterned by development at 38%). Etching was performed by putting this substrate into an etchant. Subsequently, the photoresist remaining on Au was peeled off to form a source electrode and a drain electrode made of Au.

  A positive photoresist (AZ-5206, manufactured by AZ Electronic Materials Co., Ltd.) is spin-coated on the substrate surface including the source electrode and the drain electrode, exposed through a photomask, and then tetramethylammonium hydroxide aqueous solution A photoresist pattern was formed by development at a density of 2.38%. The photoresist pattern was such that the photoresist near the source and drain electrodes was removed, and Au and the underlying substrate were exposed near the electrodes. In this state, vacuum ultraviolet rays (wavelength: 172 nm, illuminance: 3 mW / cm 2) were irradiated for 60 seconds toward the substrate on which the electrode was formed, and the vicinity of the source and drain electrodes without the photoresist was made lyophilic. As a result, the lyophobic part in the irradiated region was modified into a lyophilic part. In addition, 1.2 microliters of 25 degreeC trichlorobenzene was dripped on the lyophilic part, and as a result of measuring a contact angle by (theta) / 2 method, the contact angle was 5 degrees or less.

  Next, the above photoresist was removed by stripping (a stripping solution 106 manufactured by Tokyo Ohka Kogyo Co., Ltd.). Next, an organic semiconductor semiconductor polythiophene dissolved in trichlorobenzene at a concentration of 0.2 wt% is inkjet-applied near the lyophilic source electrode and drain electrode and placed on a hot plate at 150 ° C. for 10 minutes. Dried. At this time, the organic semiconductor layer (thickness: 40 nm) made of polythiophene is formed only on the lyophilic portion in the vicinity of the source electrode and the drain electrode from microscopic observation, and is patterned into a shape that turns over the photoresist. confirmed.

  Next, a resin (manufactured by Shin-Etsu Chemical Co., Ltd., KP-545) was spin-coated on the substrate on which polythiophene was patterned, and a gate insulating layer (thickness: 1 μm) was formed by exposure and heat curing. Further, Al was deposited on the gate insulating layer through a metal mask to form a gate electrode, thereby completing a top gate / bottom contact type organic semiconductor element.

As a result of measuring the current-voltage characteristics by changing the source / drain voltage of −50 V and the gate voltage from 20 V to −50 V, the mobility of the transistor was estimated to be 0.1 cm ² / Vs. It was. The current-voltage characteristics were measured in a vacuum and protected from light. In addition, a bias stress test was performed in which −50 V was applied to the source / drain voltage and the gate voltage for 1000 seconds, and changes in the source / drain current were observed. As a result, the current between the source electrode and the drain electrode was maintained at 85% after 1000 seconds.

  The same operation as in Example 1 was performed up to the part for preparing the substrate.

  Ag (40 nm) was formed on the entire surface of the substrate by sputtering to obtain an Ag film as a white silver film. A positive photoresist (AZ-5206, manufactured by AZ Electronic Materials Co., Ltd.) is formed on this Ag film by spin coating, and exposed with an exposure apparatus (Seiwa Optical mask aligner) through a photomask. The photoresist was patterned by development with an aqueous tetramethylammonium hydroxide solution (concentration 2.38%). Etching was performed by putting this substrate into an etchant. Subsequently, the photoresist remaining on Ag was peeled to form a source electrode and a drain electrode made of Ag.

A positive photoresist (AZ-5206, manufactured by AZ Electronic Materials Co., Ltd.) is spin-coated on the substrate surface including the source electrode and the drain electrode, exposed through a photomask, and then tetramethylammonium hydroxide aqueous solution A photoresist pattern was formed by development at a density of 2.38%. In this photoresist pattern, the photoresist near the source electrode and the drain electrode was removed, and Ag and the liquid repellent portion therebelow were exposed near the electrode. In this state, vacuum ultraviolet rays (wavelength: 172 nm, illuminance: 3 mW / cm 2) were irradiated for 60 seconds toward the substrate on which the electrode was formed, and the vicinity of the source and drain electrodes without the photoresist was denatured into a lyophilic portion. . As a result, the lyophobic portion of the irradiated region was denatured into a lyophilic portion, but at the same time, Ag as the source electrode and the drain electrode became black brown. Since the silver color changed to blackish brown, it is presumed that Ag became Ag ₂ O. In addition, 1.2 microliters of 25 degreeC trichlorobenzene was dripped on the lyophilic part, and as a result of measuring a contact angle by (theta) / 2 method, the contact angle was 5 degrees or less.

This substrate was heated in an oven at 150 ° C. for 30 minutes, and the silver oxide was thermally decomposed into oxygen and silver to reduce black brown Ag ₂ O to white silver Ag.

  Next, the above photoresist was removed by stripping (a stripping solution 106 manufactured by Tokyo Ohka Kogyo Co., Ltd.). Here, the portion to which the photoresist has adhered remains liquid repellent. Therefore, it was possible to produce a pattern having a difference in paintability within the substrate surface.

  Next, an organic semiconductor polythiophene dissolved in trichlorobenzene at a concentration of 0.2 wt% was subjected to inkjet coating (Fujifilm Dimatix) in the vicinity of the lyophilic source electrode and drain electrode, and then on a hot plate at 150 ° C. For 10 minutes to dry. At this time, the organic semiconductor layer (thickness: 40 nm) made of polythiophene is formed only on the lyophilic portion in the vicinity of the source electrode and the drain electrode from microscopic observation, and is patterned into a shape that turns over the photoresist. confirmed.

  Next, a resin (manufactured by Shin-Etsu Chemical Co., Ltd., KP-545) was spin-coated on the substrate on which polythiophene was patterned, and a gate insulating layer (thickness: 1 μm) was formed by exposure and heat curing. Further, Al was deposited on the gate insulating layer through a metal mask to form a gate electrode, thereby completing a top gate / bottom contact type organic semiconductor element.

As a result of measuring the current-voltage characteristics by changing the source / drain voltage of −50 V and the gate voltage from 20 V to −50 V, the mobility of the transistor was estimated to be 0.1 cm ² / Vs. It was. The current-voltage characteristics were measured in a vacuum and protected from light. In addition, a bias stress test was performed in which −50 V was applied to the source / drain voltage and the gate voltage for 1000 seconds, and changes in the source / drain current were observed. As a result, after 1000 seconds, the current between the source electrode and the drain electrode was maintained at 85%, and good bias stress resistance was exhibited.

  The same operation as in Example 2 was performed up to the part where the photoresist pattern was formed.

Oxygen-containing plasma was irradiated toward the substrate on which the electrode was formed, and the vicinity of the source and drain electrodes without the photoresist was denatured into a lyophilic portion. As a result, the lyophobic portion of the irradiated region was denatured into a lyophilic portion, but at the same time, Ag as the source electrode and the drain electrode became black brown. Since the silver color changed to blackish brown, it is presumed that Ag became Ag ₂ O.

After irradiation with oxygen-containing plasma, the substrate was put into an alkaline solution heated to 50 ° C., and then formalin having a formaldehyde concentration of 38% was dropped onto the substrate to reduce Ag ₂ O to Ag. Next, the above photoresist was peeled and removed. Here, the portion to which the photoresist has adhered remains liquid repellent. Therefore, it was possible to produce a pattern having a difference in wettability within the substrate surface. Next, an organic semiconductor semiconductor polythiophene dissolved in trichlorobenzene at a concentration of 0.2 wt% is inkjet-applied near the lyophilic source electrode and drain electrode and placed on a hot plate at 150 ° C. for 10 minutes. Dried. At this time, the organic semiconductor layer (thickness: 40 nm) made of polythiophene is formed only on the lyophilic portion in the vicinity of the source electrode and the drain electrode from microscopic observation, and is patterned into a shape that turns over the photoresist. confirmed.

  Next, a resin (manufactured by Shin-Etsu Chemical Co., Ltd., KP-545) was spin-coated on the substrate on which polythiophene was patterned, and a gate insulating layer (thickness: 1 μm) was formed by exposure and heat curing. Further, Al was deposited on the gate insulating layer through a metal mask to form a gate electrode, thereby completing a top gate / bottom contact type organic semiconductor element.

As a result of measuring the current-voltage characteristics by changing the source / drain voltage of −50 V and the gate voltage from 20 V to −50 V, the mobility of the transistor was estimated to be 0.1 cm ² / Vs. It was. The current-voltage characteristics were measured in a vacuum and protected from light. In addition, a bias stress test was performed in which −50 V was applied to the source / drain voltage and the gate voltage for 1000 seconds, and changes in the source / drain current were observed. As a result, after 1000 seconds, the current between the source electrode and the drain electrode was maintained at 60%, and good bias stress resistance was exhibited.

Comparative example

  The same operation as in Example 2 was performed up to the portion irradiated with vacuum ultraviolet rays.

  Next, the photoresist was removed by stripping (a stripping solution 106 manufactured by Tokyo Ohka Kogyo Co., Ltd.). Next, a solution obtained by dissolving polythiophene in trichlorobenzene at a concentration of 0.2 wt% is inkjet-applied in the vicinity of the source electrode and drain electrode modified into a lyophilic portion, and placed on a hot plate at 150 ° C. for 10 minutes to form a film. Was dried. At this time, it was confirmed from microscopic observation that a polythiophene film (40 nm) was formed only on the lyophilic portion in the vicinity of the source electrode and the drain electrode, and was patterned into a shape that would reverse the photoresist film.

  Resin (KP-545, manufactured by Shin-Etsu Chemical Co., Ltd.) was spin-coated on the substrate on which polythiophene patterning was completed, and a gate insulating layer (thickness: 1 μm) was formed by UV exposure and heat curing. Further, Al was deposited on the gate insulating layer through a metal mask to form a gate electrode, thereby completing a top gate / bottom contact type organic semiconductor element.

  The current-voltage characteristics were measured by changing the source / drain voltage of −50 V and the gate voltage from 20 V to −50 V for the fabricated organic semiconductor element. However, the electrical characteristics can be obtained because the electrodes are oxidized. There wasn't.

DESCRIPTION OF SYMBOLS 1 ... Base | substrate 2 ... Liquid repellent part 3 ... Source electrode 4 ... Drain electrode 5 ... Shielding layer 6 ... Organic-semiconductor element substrate 7 ... Lipophilic part 8 ... Organic-semiconductor layer 9 ... Gate insulating layer 10 ... Gate electrode 11 ... Base material DESCRIPTION OF SYMBOLS 12 ... Ultraviolet or oxygen-containing plasma 13 ... Oxidized source electrode 14 ... Oxidized drain electrode

Claims (2)

A substrate having a liquid repellent portion having liquid repellency with respect to an organic semiconductor layer forming solution containing an organic semiconductor material in a solvent, a source electrode and a drain electrode formed on the substrate, and a liquid repellency of the substrate And a source of the organic semiconductor element substrate on the organic semiconductor element substrate, wherein the source electrode and the drain electrode contain gold or / and platinum. By irradiating the substrate for an organic semiconductor element with ultraviolet light or oxygen-containing plasma from the side on which the electrode and drain electrode are formed, and using the shielding layer, a part of the liquid repellent portion of the substrate is the organic semiconductor. A step of forming a substrate for an organic semiconductor element that is modified into a pattern in a lyophilic part that is lyophilic with respect to the layer forming solution;
Wherein the shielding layer is removed from the base of the substrate for the organic semiconductor element, wherein the organic semiconductor layer forming solution was applied to the organic semiconductor device on the substrate for, organic semiconductor that Sessu to the source electrode and the drain electrode Forming an organic semiconductor layer for forming the layer. A substrate having a liquid repellent portion having liquid repellency with respect to an organic semiconductor layer forming solution containing an organic semiconductor material in a solvent, a source electrode and a drain electrode formed on the substrate, and a liquid repellency of the substrate An organic semiconductor element substrate having a shielding layer formed on a part of the portion, and in which one or both of the source electrode and the drain electrode contains a metal having a redox potential of silver or less. In the atmosphere containing the organic semiconductor element substrate, the organic semiconductor element substrate is irradiated with ultraviolet rays or oxygen-containing plasma from the side where the source electrode and the drain electrode are formed, and the shielding layer is used. A step of forming a substrate for an organic semiconductor element, in which a part of the liquid repellent portion of the base is modified into a lyophilic portion having lyophilicity with respect to the organic semiconductor layer forming solution;
A reduction step of the source electrode and the drain electrode for reducing a metal whose oxidation-reduction potential contained in the source electrode and the drain electrode is lower than silver; and
Wherein the shielding layer is removed from the base of the substrate for the organic semiconductor element, wherein the organic semiconductor layer forming solution was applied to the organic semiconductor device on the substrate for, organic semiconductor that Sessu in the source electrode and said drain electrode Forming an organic semiconductor layer for forming the layer.

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