JP2007019121A - Substrate for manufacturing organic semiconductor device, organic semiconductor device, and method for manufacturing same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate for manufacturing an organic semiconductor device by which an organic semiconductor film having a higher orientation order can be formed more easily and efficiently, and also to provide an organic semiconductor device using the same and method for manufacturing the same. <P>SOLUTION: The substrate for manufacturing the organic semiconductor device includes a substrate, a gate electrode formed on the substrate, a gate insulation film formed on the gate electrode, and an organic thin film formed on the gate insulation film. The organic thin film is formed from a solution for forming an organic thin film which contains: a silane-based surfactant expressed by the formula (1) R<SB>n</SB>-Si-X<SB>4-n</SB>(wherein R is 1-20C hydrocarbon or the like which may include a substituent, X is hydroxyl or the like, and n is an integer from 1 to 3); and a catalyst which can interact with the silane-based surfactant. The organic semiconductor device includes the substrate, and a source electrode, a drain electrode, a semiconductor film, and a protection film which are formed on the substrate. The method of manufacturing the organic semiconductor device is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an organic semiconductor device forming substrate capable of easily and efficiently forming an organic semiconductor film having a high orientation order, an organic semiconductor device using the substrate, and a method for manufacturing the organic semiconductor device.

  An organic semiconductor device (hereinafter sometimes referred to as “organic TFT”) includes a substrate, a gate electrode, an insulating film, a drain electrode, a source electrode, an organic semiconductor film, and the like.

  The organic TFT changes the amount of current flowing between the drain electrode and the source electrode by modulating the amount of carriers accumulated at the interface between the insulating film and the organic semiconductor film from the excess state to the insufficient state by the voltage applied to the gate electrode. Thus, a switching operation is performed.

  By the way, in order to obtain a high switching operation with these organic semiconductor films, in the organic semiconductor film formed on the surface of the insulating film, the organic semiconductor molecules are arranged in a close-packed manner so that the directions of the organic semiconductor molecules are aligned with each other (that is, a high orientation order). It is necessary to form an organic semiconductor film).

  Conventionally, as a method of forming an organic semiconductor film having such a high orientation order, a method in which the surface of an insulating film is previously coated with an organic thin film (also referred to as “self-assembled monomolecular film” or “SAM film”) is known. It has been.

For example, in Non-Patent Document 1, when the surface of an insulating film made of a silicon thermal oxide film is coated with a self-assembled monomolecular film such as octadecyltrichlorosilane (OTS), the orientation order of the organic semiconductor film made of F8T2 semiconductor polymer is described. It is described that the switching performance is improved.
In Non-Patent Document 2, when the surface of the insulating film made of a silicon thermal oxide film is coated with OTS, the orientation order of the organic semiconductor film in which the pentacene semiconductor small molecules are deposited by the vacuum deposition method is improved, and the orientation order is high. It has been reported that the crystal grain size of the TFT increases as compared with the case where the OTS coating is not performed, thereby improving the switching performance of the TFT.
Further, in Non-Patent Document 3, the field effect mobility of an organic semiconductor film in which the surface of an insulating film is previously coated with an organic thin film made of hexamethyldisilazane and then P3HT is applied thereon is 0.01 to 0. 0. It has been reported to improve to 1 cm ² / Vs.

  As described above, when an organic semiconductor film is formed on the surface of an insulating film previously modified with an organic thin film, the alignment order of the organic semiconductor film is improved and switching performance is improved. An organic TFT having equivalent or better performance can be obtained.

  However, in such an organic TFT, if the insulating film surface is modified with an organic thin film in order to improve the alignment order of the organic semiconductor molecules and improve the switching performance, the light leakage current increases, and the coating is performed thereon. There was a problem that electrodes could not be finely formed by the process.

  In order to solve this problem, Non-Patent Document 4 and Patent Documents 1 and 2 describe an organic semiconductor comprising a gate electrode, a gate insulating film, a source electrode, a drain electrode, a semiconductor film, and a protective film stacked on a substrate. In the apparatus, a self-assembled monomolecular film is interposed at the interface between the semiconductor film and the insulating film formed in the gate electrode projection region on the surface of the insulating film, and at the interface between the semiconductor film and the insulating film formed outside the region. Has proposed an organic semiconductor device characterized in that no self-assembled monolayer is present.

According to the organic semiconductor device described in this document, a self-assembled monomolecular film is disposed only in the gate electrode projection region on the surface of the insulating film, and only the organic semiconductor film portion in the region is selectively aligned. The on-current can be increased without increasing the light leakage current, and the switching performance can be improved.
A, Salleo et al., Applied Physics Letters 81 (23), pp. 4383-4385 (2002) Y. Y. Lin et al., IEEE Trans. Electron. Devices, 44, pp. 1325-1331 (1997) H. Sirringhaus et al., SCIENCE, Vol. 280, pp. 1741-1743 (1998) E-Express, July 15, 2004, pages 37-43 JP 2001-94107 A JP 2005-79560 A

  An object of the present invention is to provide a substrate for forming an organic semiconductor device that can easily and efficiently form an organic semiconductor film having a high orientation order, an organic semiconductor device using the substrate, and a method for manufacturing the organic semiconductor device. To do.

  As a result of diligent research to solve the above problems, the inventors of the present invention sequentially formed a gate electrode and a gate insulating film on a substrate, and further, a specific silane-based surfactant and the silane on the gate insulating film. An organic thin film was formed from an organic thin film forming solution containing a catalyst capable of interacting with a surfactant. Next, a photoresist is formed on the organic thin film, the photoresist is exposed from the back side of the substrate using the gate electrode as a photomask, and similarly, the organic thin film is etched by oxygen plasma treatment to form the surface of the gate insulating film. An organic semiconductor device manufacturing substrate having a structure having an organic thin film only in the gate electrode projection region was obtained. Furthermore, when this organic semiconductor device manufacturing substrate is used, it has been found that an organic semiconductor film having a high orientation order can be formed on the organic thin film of the substrate, and the present invention has been completed.

Thus, according to the first aspect of the present invention, there is provided the organic semiconductor device manufacturing substrate according to any one of (1) to (8) below.
(1) A substrate for manufacturing an organic semiconductor device, comprising: a substrate; a gate electrode formed on the substrate; a gate insulating film formed on the gate electrode; and an organic thin film formed on the gate insulating film. a is, the organic thin film is of the formula _(1): R n in _{-Si-X 4-n} (wherein, R represents a hydrocarbon group having C1~20 which may have a substituent, have a substituent Represents a C1-20 halogenated hydrocarbon group, a C1-20 hydrocarbon group containing a linking group, or a C1-20 halogenated hydrocarbon group containing a linking group, wherein X is a hydroxyl group, a halogen atom , A C1-6 alkoxy group or an acyloxy group, n represents an integer of 1 to 3), and an organic thin film comprising a catalyst capable of interacting with the silane surfactant It is an organic thin film formed from a forming solution. A substrate for manufacturing organic semiconductor devices.

(2) The catalyst is a metal oxide; a metal hydroxide; a metal alkoxide; a chelated or coordinated metal compound; a metal alkoxide partial hydrolysis product; The substrate for manufacturing an organic semiconductor device according to (1), which is at least one selected from a hydrolysis product obtained by treatment with at least double equivalent water; an organic acid; a silanol condensation catalyst; and an acid catalyst. .
(3) The catalyst comprises (a) a metal oxide; a metal hydroxide; a metal alkoxide; a chelated or coordinated metal compound; a metal alkoxide partial hydrolysis product; a metal alkoxide as the metal alkoxide. A hydrolyzate obtained by treating with water at least twice the equivalent of the above; organic acid; silanol condensation catalyst; and at least one selected from acid catalysts, and (b) containing the silane-based surfactant The substrate for manufacturing an organic semiconductor device according to (1), which is a composition.
(4) The substrate for manufacturing an organic semiconductor device according to (2) or (3), wherein the metal alkoxide is a titanium alkoxide.

(5) The substrate for manufacturing an organic semiconductor device according to (4), wherein the titanium alkoxide is titanium tetraisopropoxide.
(6) The organic semiconductor device manufacturing substrate according to any one of (1) to (5), wherein the organic thin film forming solution is a hydrocarbon solvent solution.
(7) The substrate for manufacturing an organic semiconductor device according to (6), wherein the hydrocarbon solvent is toluene.
(8) The organic semiconductor device manufacturing method according to any one of (1) to (7), wherein the water content in the solution for forming an organic thin film is within the range of the saturated water content from 50 ppm to the organic solvent. substrate.

According to a second aspect of the present invention, there is provided an organic semiconductor device according to any one of the following (9) to (18).
(9) In an organic semiconductor device composed of a gate electrode, a gate insulating film, a source electrode, a drain electrode, a semiconductor film and a protective film stacked on a substrate, the semiconductor film is composed of an aggregate of organic semiconductor molecules. At the interface between the semiconductor film and the insulating film formed in the gate electrode projection region on the surface of the insulating film, the formula (1): R _n -Si-X _4-n (wherein R represents a substituent) A C1-20 hydrocarbon group optionally having a substituent, a C1-20 halogenated hydrocarbon group optionally having a substituent, a C1-20 hydrocarbon group including a linking group, or a linking group. A C1-20 halogenated hydrocarbon group, X represents a hydroxyl group, a halogen atom, a C1-6 alkoxy group or an acyloxy group, and n represents an integer of 1 to 3). And the silane-based surfactant An organic semiconductor device comprising an organic thin film formed from an organic thin film forming solution containing a catalyst capable of interacting with the organic semiconductor device.

(10) The organic semiconductor device according to (9), wherein the organic thin film is not interposed at an interface between the semiconductor film and the gate insulating film formed outside the region.
(11) The alignment order of the organic semiconductor molecules in the semiconductor film portion formed in the gate electrode projection region on the surface of the insulating film is higher than the alignment order in the semiconductor film portion formed outside the region. The organic semiconductor device according to (9) or (10).
(12) The catalyst is a metal oxide; a metal hydroxide; a metal alkoxide; a chelated or coordinated metal compound; a metal alkoxide partial hydrolysis product; Any one of (9) to (11), characterized in that it is at least one selected from a hydrolysis product obtained by treating with double equivalent or more of water; an organic acid; a silanol condensation catalyst; and an acid catalyst. The organic semiconductor device described in 1.

(13) The catalyst comprises: (a) a metal oxide; a metal hydroxide; a metal alkoxide; a chelated or coordinated metal compound; a metal alkoxide partial hydrolysis product; A hydrolyzate obtained by treating with water at least twice the equivalent of the above; organic acid; silanol condensation catalyst; and at least one selected from acid catalysts, and (b) containing the silane-based surfactant It is a composition, The organic-semiconductor device in any one of (9)-(11) characterized by the above-mentioned.
(14) The organic semiconductor device according to (12) or (13), wherein the metal alkoxide is a titanium alkoxide.
(15) The organic semiconductor device according to (14), wherein the titanium alkoxide is titanium tetraisopropoxide.

(16) The organic semiconductor device according to any one of (9) to (15), wherein the organic thin film forming solution is a hydrocarbon solvent solution.
(17) The organic semiconductor device according to (16), wherein the hydrocarbon solvent is toluene.
(18) The organic semiconductor device according to any one of (9) to (17), wherein the water content in the solution for forming an organic thin film is within the range of the saturated water content from 50 ppm to the organic solvent.

According to 3rd aspect of this invention, the manufacturing method of the organic-semiconductor device in any one of following (19)-(21) is provided.
(19) The organic semiconductor device forming substrate according to any one of (1) to (8) is irradiated with light from the substrate surface through a photomask to form a semiconductor film outside the gate electrode projection region. An organic semiconductor device manufacturing method comprising removing an organic thin film from a region.
(20) A semiconductor film outside the gate electrode projection region is formed on the organic semiconductor device forming substrate according to any one of (1) to (8) above by irradiating light from the back surface of the substrate using the gate electrode as a photomask. A method of manufacturing an organic semiconductor device, comprising removing an organic thin film from a region to be manufactured.
(21) A plate-like transparent support having a photocatalyst layer formed from a photocatalyst layer-forming composition containing at least titanium oxide on one surface side, the photocatalyst layer side facing the organic thin film side, and the substrate The photocatalyst is superposed, or the photocatalyst layer side is opposed to the substrate at a predetermined interval facing the substrate on which the organic thin film is formed, and active energy rays are irradiated from the other surface side of the support. A method for producing an organic semiconductor device, wherein active species are generated by a reaction, and the surface of the organic thin film is modified with a predetermined pattern by the active species, and then only the irradiated portion of the organic thin film is decomposed and removed.

  According to the present invention, an organic thin film including the silane-based surfactant represented by the formula (1) and a catalyst capable of interacting with the silane-based surfactant is formed only in the gate electrode projection region on the insulating film surface. By disposing the organic thin film formed from the solution for use, only the organic semiconductor film portion in the region can be selectively improved in the alignment order. For this reason, the alignment order of the organic semiconductor film part irradiated with light (outside the gate electrode projection area on the insulating film surface) is not improved, the on-current can be increased without increasing the light leakage current, and the switching performance is improved. can do.

Further, the drain disposed in a self-aligned manner with respect to the gate electrode by utilizing the lyophobic action of the organic thin film selectively and precisely disposed only within the gate electrode projection region on the surface of the insulating film as described above. / The source electrode can be formed with high definition by a coating process.
In this way, it is possible to manufacture a high-performance and high-definition organic semiconductor device with high productivity and low manufacturing cost.

Hereinafter, the present invention will be described in detail.
1) Organic Semiconductor Device Manufacturing Substrate The organic semiconductor device manufacturing substrate of the present invention includes a substrate, a gate electrode formed on the substrate, a gate insulating film formed on the gate electrode, and the gate insulating film. An organic semiconductor device manufacturing substrate having an organic thin film formed thereon, wherein the organic thin film has the formula (1): R _n -Si-X _4-n (wherein R has a substituent). A C1-20 hydrocarbon group optionally having a substituent, a C1-20 halogenated hydrocarbon group optionally having a substituent, a C1-20 hydrocarbon group containing a linking group, or a C1-20 containing a linking group. 20 represents a halogenated hydrocarbon group, X represents a hydroxyl group, a halogen atom, a C1-6 alkoxy group or an acyloxy group, and n represents an integer of 1 to 3), and Catalyst capable of interacting with the silane-based surfactant Characterized in that an organic thin film formed from an organic thin film forming solution containing.

FIG. 1 shows a cross section of the layer structure of the substrate 10 for manufacturing an organic semiconductor device of the present invention.
In FIG. 1, 1 is a substrate, 2 is a gate electrode, 3 is an insulating film (gate insulating film), and 4 is an organic thin film. Moreover, the manufacturing process sectional drawing of the board | substrate for organic-semiconductor device manufacture of this invention is shown in FIG.
Hereinafter, the substrate for manufacturing an organic semiconductor device of the present invention will be described with reference to FIGS.

First, the substrate 1 is prepared. The substrate 1 used in the present invention is not particularly limited as long as it is made of an insulating material. Examples of the substrate material include inorganic materials such as glass and alumina sintered bodies; various insulating plastics such as polyimide, polyester, polyethylene, polyphenylene sulfide, and polyparaxylene. The substrate used in the present invention is a single layer and may be a laminate of two or more layers.
There is no particular limitation on the thickness and size of the substrate, and a conventionally known thickness and size substrate can be used.

Next, as shown in FIG. 2A, a gate electrode 2 is formed in a predetermined region on the surface of the substrate 1.
Materials for the gate electrode 2 include organic materials such as polyaniline, polythiophene, and conductive ink; metals such as gold, platinum, chromium, palladium, aluminum, indium, molybdenum, and nickel; alloys using these metals; polysilicon And silicon such as amorphous silicon; metal oxides such as tin oxide, indium oxide, and indium tin oxide (ITO); These can be used individually by 1 type or in combination of 2 or more types.

The method for forming the gate electrode 2 is not particularly limited, and an existing thin film forming method can be employed. For example, when the organic material or conductive ink is used, a spin coating method, a casting method, a pulling method, a dipping method, a vacuum deposition method, or the like can be employed. When metals, alloys, silicons, metal oxides, etc. are used, vacuum evaporation, electron beam evaporation, reactive evaporation, ion plating, sputtering, thermal CVD, plasma CVD A reactive CVD method can be employed. An existing photolithography method and a dry etching method or a wet etching method can be used for the patterning process for forming the electrode.
The film thickness of the gate electrode 2 is usually about 50 to 300 nm.

Next, as shown in FIG. 2B, an insulating film (gate insulating film) 3 is formed so as to cover at least the gate electrode 2.
As materials used for forming the insulating film 3, organic materials such as polychloropyrene, polyethylene terephthalate, polyoxymethylene, polyvinyl chloride, polyvinylidene fluoride, cyanoethyl pullulan, polymethyl methacrylate, polysulfone, polycarbonate, polyimide, perfluoropolyether; Inorganic materials such as SiO ₂ , SiNx, Al ₂ O ₃ ; These can be used individually by 1 type or in combination of 2 or more types.

The method for forming the insulating film 3 is not particularly limited, and an existing thin film forming method can be employed. For example, when the organic material is used, a spin coating method, a casting method, a pulling method, a dipping method, a vacuum deposition method, or the like can be employed. In addition, when an inorganic material is used, a vacuum vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, a sputtering method, a thermal CVD method, a plasma CVD method, a reactive CVD method, etc. may be employed. it can.
The film thickness of the insulating film 3 is usually about 100 to 1000 nm.

Next, as shown in FIG. 2 (c), the formula (1): the silane surfactant represented by _{R n -Si-X 4-n} , and a catalyst capable of interacting with the silane-based surfactant The organic thin film 4 is formed using the organic thin film forming solution.

The organic thin film forming solution used for forming the organic thin film is composed of a silane-based surfactant represented by the formula (1): R _n —Si—X _4-n and a catalyst capable of interacting with the silane-based surfactant. Including.
In the formula (1), R is a C1-20 hydrocarbon group which may have a substituent, a C1-20 halogenated hydrocarbon group which may have a substituent, and a C1 containing a linking group. -20 hydrocarbon group or a C1-20 halogenated hydrocarbon group containing a linking group.

  Examples of the hydrocarbon group of the C1-20 hydrocarbon group which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. , T-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-decyl group, n-octadecyl group, etc. An alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, a pentynyl group, an n-decynyl group, and an n-octadecynyl group; an aryl such as a phenyl group or a naphthyl group A C8-20 hydrocarbon group is preferable.

  Examples of the halogenated hydrocarbon group of the halogenated hydrocarbon group which may have a substituent include a halogenated alkyl group having 1 to 20 carbon atoms, a halogenated alkenyl group having 2 to 20 carbon atoms, and a halogenated aryl group. Etc. Specific examples include groups in which one or more hydrogen atoms in the hydrocarbon groups exemplified above are substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

  Examples of the substituent of the hydrocarbon group that may have a substituent or the halogenated hydrocarbon group that may have a substituent include a carboxyl group; an amide group; an imide group; an ester group; a methoxy group, and an ethoxy group. An alkoxy group such as a group; or a hydroxyl group. The number of these substituents is preferably 0-3.

  Specific examples of the hydrocarbon group including a linking group include the same hydrocarbon groups as those described above as the hydrocarbon group of the hydrocarbon group which may have a substituent.

  In addition, as the halogenated hydrocarbon group of the halogenated hydrocarbon group containing a linking group, specifically, those listed as the halogenated hydrocarbon group of the halogenated hydrocarbon group which may have the above substituent The same thing can be mentioned.

The linking group is preferably present between a carbon-carbon bond of a hydrocarbon group or a halogenated hydrocarbon group, or between carbon of a hydrocarbon group and Si. Specific examples of the linking group include —O—, —S—, —SO ₂ —, —CO—, —C (═O) O—, and the like.
n represents an integer of 1 to 3, and is preferably 1.

X represents a hydroxyl group, a halogen atom, a C1-6 alkoxy group or an acyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. And methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group and the like. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, and an n-butylcarbonyloxy group.
Among these, C1-6 alkoxy groups are preferred,

  Specific examples of the silane surfactant represented by the formula (1) include (heptadecafluorin-1,1,2,2-tetrahydrodecyl) -1-triethoxysilane, (heptadecafluorin-1). , 1,2,2-tetrahydrodecyl) -1-trichlorosilane, (heptadecafluorine-1,1,2,2-tetrahydrodecyl) -1-dimethylchlorosilane, or n-octadecyltrimethoxysilane. . Of these, n-octadecyltrimethoxysilane is particularly preferable.

  The catalyst capable of interacting with the silane surfactant is hydrolyzable by interacting with the silane part or hydrolyzable group part of the silane surfactant via a coordination bond or a hydrogen bond. The compound is not particularly limited as long as it has a function of activating a group or a hydroxyl group and promoting condensation. For example, (A) a metal oxide, a metal hydroxide, a metal alkoxide, a chelated or coordinated metal compound, a metal alkoxide partial hydrolysis product, and a metal alkoxide equivalent to twice the metal alkoxide At least one compound selected from the group consisting of hydrolysis products obtained by treatment with water, organic acids, silanol condensation catalysts, and acid catalysts (hereinafter, also referred to as “catalyst A component”), (B) A composition containing the catalyst A component and the silane-based surfactant (hereinafter sometimes referred to as “catalyst B component”) is preferable, and the metal alkoxides and the partial hydrolysis products of the metal alkoxides are preferred. It is more preferable to use at least one kind.

  Although it does not specifically limit as metal alkoxides, it consists of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, and lead because the organic thin film excellent in transparency can be obtained. At least one metal alkoxide selected from the group is preferred, and titanium alkoxides such as titanium tetraisopropoxide are more preferred. Moreover, although carbon number of the alkoxy group of metal alkoxides is not specifically limited, C1-C4 is more preferable from the content oxide density | concentration, the detachment | desorption ease of an organic substance, availability, etc.

Specific examples of the metal alkoxides used in the present invention include Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ -i) ₄ , Si (OC ₄ H ₉ ) _{4 and the} like. Silicon alkoxides; titanium alkoxides such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ -i) ₄ , Ti (OC ₄ H ₉ ) ₄ ; Ti [OSi (CH ₃ ) _{3] 4, Ti [OSi (} C 2 H 5) tetrakis trialkylsiloxy titanium such as _{3] 4; Zr (OCH 3} ) 4, Zr (OC 2 H 5) 4, Zr (OC 3 H 7 -i) 4 Zr (OC ₄ H ₉ ) ₄ and other zirconium alkoxides; Al (OCH ₃ ) ₃ , Al (OC ₂ H ₅ ) ₃ , Al (OC ₃ H ₇ -i) ₃ , Al (OC ₄ H ₉ ) _{3 and the} like Aluminum Indium alkoxides; In (OCH ₃ ) ₃ , In (OC ₂ H ₅ ) ₃ , In (OC ₃ H ₇ -i) ₃ , In (OC ₄ H ₉ ) _3, etc. Indium alkoxides; Sn (OCH ₃ ) ₄ , Tin alkoxides such as Sn (OC ₂ H ₅ ) ₄ , Sn (OC ₃ H ₇ -i) ₄ , Sn (OC ₄ H ₉ ) ₄ ; Ta (OCH ₃ ) ₅ , Ta (OC ₂ H ₅ ) ₅ , Ta Tantalum alkoxides such as (OC ₃ H ₇ -i) ₅ and Ta (OC ₄ H ₉ ) ₅ ; W (OCH ₃ ) ₆ , W (OC ₂ H ₅ ) ₆ , W (OC ₃ H ₇ -i) ₆ , W _{(OC 4} H _{9) 6} tungsten alkoxides such _{as; Zn (OCH 3) 2,} Zn (OC 2 H 5) zinc, such as _{2 alkoxide; Pb (OC 4 H 9)} 4 lead alkoxides such as; and the like These metal alkoxides can be used alone or in combination of two or more.

  In the present invention, as a metal alkoxide, a reaction of a composite alkoxide obtained by reaction of two or more metal alkoxides, one or more metal alkoxides, and one or two or more metal salts. It is also possible to use a composite alkoxide obtained by the above and a combination thereof.

  The composite alkoxide obtained by the reaction of two or more kinds of metal alkoxides includes a complex alkoxide obtained by the reaction of an alkali metal or alkaline earth metal alkoxide and a transition metal alkoxide, or a complex salt by a combination of Group 3B elements. The compound alkoxide obtained by the form of this can be illustrated.

Specific _{examples, BaTi (OR ') 6,} SrTi (OR') 6, BaZr (OR ') 6, SrZr (OR') 6, LiNb (OR ') 6, LiTa (OR') 6 and, A combination of two or more of these, LiVO (OR ′) ₄ , MgAl ₂ (OR ′) ₈ , (OR ′) ₃ SiOAl (OR ″) ₂ , (OR ′) ₃ SiOTi (OR ″) ₃ , (OR ′) ₃ SiONb (OR ″) ₃ , (OR ′) ₃ SiOTa (OR ″) _4, etc., reaction products of silicon alkoxides with other metal alkoxides, condensation polymers thereof, and the like. Here, R ′ and R ″ represent an alkyl group or the like.

  Examples of the composite alkoxide obtained by reaction of one or more metal alkoxides with one or more metal salts include compounds obtained by reaction of metal salts with metal alkoxides. .

  Examples of metal salts include hydrochlorides, nitrates, sulfates, acetates, formates, oxalates, and the like, and examples of metal alkoxides are the same as those described above.

  The partial hydrolysis product of the metal alkoxide is obtained before the metal alkoxide is completely hydrolyzed and exists in an oligomer state.

  As a method for producing a partial hydrolysis product of a metal alkoxide, 0.5 to 2.0 times less water than the above exemplified metal alkoxide is used in an organic solvent, and the organic solvent reflux temperature is from −100 ° C. A method of hydrolyzing within a range can be preferably exemplified.

In particular,
(I) A method of adding water in an amount of less than 0.5 to 1.0 times mol of the metal alkoxide in an organic solvent,
(Ii) In an organic solvent, the temperature is less than the temperature at which hydrolysis starts, preferably 0 ° C. or less, more preferably in the range of −20 to −100 ° C. How to add water,
(Iii) A metal alkoxide while controlling the hydrolysis rate by a method of controlling the rate of water addition in an organic solvent or a method of using an aqueous solution in which a water-soluble solvent is added to water to reduce the water concentration. Examples include a method of adding 0.5 to 2.0-fold moles of water at room temperature to the kind.

  In the above method (i), after adding a predetermined amount of water at an arbitrary temperature, the reaction can be carried out by further adding water at a temperature not higher than the temperature at which hydrolysis starts, preferably at -20 ° C or lower. .

  The reaction of the metal alkoxide with water can be carried out by directly mixing the metal alkoxide with water without using an organic solvent, but it is preferably carried out in an organic solvent. Specifically, a method of adding water diluted with an organic solvent to an organic solvent solution of a metal alkoxide; a method of adding a metal alkoxide or an organic solvent solution thereof into an organic solvent in which water is suspended or dissolved; Any of these methods can be used, and the former method in which water is added later is preferable.

  The concentration of the metal alkoxides in the organic solvent is not particularly limited as long as it has a fluidity capable of suppressing rapid heat generation and can be stirred, but is usually in the range of 5 to 30% by weight.

  The reaction temperature between the metal alkoxide and water in the method (i) is not particularly limited, and is usually eliminated in the range of −100 to + 100 ° C., preferably from −20 ° C. by the organic solvent or hydrolysis. The temperature range is up to the boiling point of the alcohol.

  The temperature at which water is added in the method (ii) depends on the stability of the metal alkoxide, and is not particularly limited as long as it is a hydrolysis start temperature or lower or 0 ° C. or lower. Depending on the type, it is preferable to add water to the metal alkoxide in a temperature range of −50 ° C. to −100 ° C. In addition, after adding water at a low temperature and aging for a certain period of time, hydrolysis can be performed at the reflux temperature of the solvent used from room temperature, and a dehydration condensation reaction can also be performed.

  The reaction of the metal alkoxides with water in the method (iii) above can be performed without using a special cooling device, for example, by controlling the rate of water addition in a temperature range that can be cooled, for example, in the range of 0 ° C. to room temperature. The hydrolysis rate can be controlled by a method other than the above temperature. After aging for a certain period of time, hydrolysis can be performed from room temperature to the reflux temperature of the solvent used, and a dehydration condensation reaction can also be performed.

  As the organic solvent to be used, it is preferable that the hydrolysis product of the metal alkoxide can be dispersed as a dispersoid in the organic solvent, and the reaction of treating the silane surfactant with water at a low temperature. A solvent that has high water solubility and does not solidify at low temperatures is more preferable because it can be performed.

  Specific examples of the organic solvent used include alcohol solvents such as methanol, ethanol and isopropanol; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene and xylene. Ether solvents such as tetrahydrofuran, diethyl ether and dioxane; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; amide solvents such as dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; methyl polysiloxane , Silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, and methylphenylpolysiloxane (Japanese Patent Laid-Open No. 9-208438). ), And the like; can be mentioned.

These solvents can be used alone or in combination of two or more.
When used as a mixed solvent, a combination of a hydrocarbon solvent such as toluene or xylene and a lower alcohol solvent system such as methanol, ethanol, isopropanol, or t-butanol is preferable. In this case, the lower alcohol solvent is more preferably a secondary or higher alcohol solvent such as isopropanol or t-butanol. The mixing ratio of the mixed solvent is not particularly limited, but it is preferable to use a hydrocarbon solvent and a lower alcohol solvent in a volume ratio of 99/1 to 50/50.

  The water to be used is not particularly limited as long as it is neutral, but it is preferable to use pure water, distilled water or ion-exchanged water from the viewpoint of obtaining a fine organic thin film with few impurities. The usage-amount of water is 0.5-2.0 times mole with respect to 1 mol of said metal alkoxides.

  In the partial hydrolysis reaction of metal alkoxides with water, an acid, a base, or a dispersion stabilizer may be added. Acids and bases were produced as a deflocculant for redispersing the precipitate formed by condensation, and as a catalyst for producing dispersoids such as colloidal particles by hydrolyzing and dehydrating metal alkoxides. There is no particular limitation as long as it functions as a dispersoid dispersant.

  Examples of acids used include mineral acids such as hydrochloric acid, nitric acid, boric acid, and borofluoric acid; organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid; diphenyliodonium And a photoacid generator that generates an acid by light irradiation, such as hexafluorophosphate and triphenylphosphonium hexafluorophosphate.

  Examples of the base used include triethanolamine, triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, ammonia, dimethylformamide, and phosphine.

  The dispersion stabilizer is an agent having the effect of stably dispersing the dispersoid in the dispersion medium, and examples thereof include anti-caking agents such as a peptizer, a protective colloid, and a surfactant. Specifically, polyhydric carboxylic acids such as glycolic acid, gluconic acid, lactic acid, tartaric acid, citric acid, malic acid and succinic acid; hydroxycarboxylic acids; phosphoric acids such as pyrophosphoric acid and tripolyphosphoric acid; acetylacetone, methyl acetoacetate, aceto Ethyl acetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptane Multidentate ligand compounds having strong chelating ability for metal atoms such as dione, 2,4-octanedione, 2,4-nonanedione, 5-methylhexanedione; Sulperus 3000, 9000, 17000, 20000, 24000 ( As mentioned above, manufactured by Zeneca), Disperbyk-161, -162, -16 , -164 (above, manufactured by Vick Chemie), aliphatic amine series, hydrostearic acid series, polyester amine; dimethylpolysiloxane, methyl (polysiloxyalkylene) siloxane copolymer, trimethylsiloxysilicic acid, carboxy-modified silicone oil, Examples thereof include silicone compounds such as amine-modified silicone (JP-A-9-208438, JP-A-2000-53421, etc.).

  The partial hydrolysis product obtained as described above becomes a dispersoid having a property of stably dispersing without aggregation in an organic solvent in the absence of an acid, a base and / or a dispersion stabilizer. ing. In this case, the dispersoid refers to fine particles dispersed in the dispersion system, and specific examples include colloidal particles.

  Here, the state of being stably dispersed without agglomeration means that the dispersoid of the hydrolysis product is condensed and heterogeneous in the absence of an acid, a base and / or a dispersion stabilizer in an organic solvent. It represents a state where they are not separated, and preferably represents a transparent and homogeneous state.

  Transparent means a state in which the transmittance in visible light is high. Specifically, the concentration of the dispersoid is 0.5% by weight in terms of oxide, the optical path length of the quartz cell is 1 cm, and the control sample is organic. This is a state that represents a transmittance of 80 to 100%, preferably expressed as a spectral transmittance measured under the condition of using a solvent and a light wavelength of 550 nm.

  The particle size of the dispersoid of the partial hydrolysis product is not particularly limited, but is usually in the range of 1 to 100 nm, preferably 1 to 50 nm, more preferably 1 to 10 nm in order to obtain high transmittance in visible light. .

  The catalyst B component as a catalyst capable of interacting with the silane-based surfactant can be obtained by mixing the catalyst A component and the silane-based surfactant, and more specifically, the silane-based surfactant. The agent can be prepared by treating with water in an organic solvent in the presence of catalyst A component. In the catalyst B component, the silane-based surfactant is preferably contained in an amount of 0.5 to 2.0 mol, more preferably 0.8 to 1.5 mol, relative to 1 mol of the catalyst A component.

  As a method of treating the silane-based surfactant with water in the presence of the catalyst A component in an organic solvent, specifically, (a) water is added to the organic solvent solution of the silane-based surfactant and the catalyst A component. And (i) a method of adding the catalyst A component to an organic solvent solution of a silane-based surfactant and water. The catalyst A component is generally used in the state of an organic solvent containing water.

As the organic solvent used for the preparation of the catalyst B component, hydrocarbon solvents, fluorocarbon solvents and silicone solvents are preferable, and those having a boiling point of 100 to 250 ° C are more preferable. Specifically, hydrocarbon solvents such as n-hexane, cyclohexane, benzene, toluene, xylene, petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, ligroin; CBr _{2 ClCF 3, CClF 2 CF 2} CC1 3, CClF 2 CF 2 CHFCl, CF 3 CF 2 CHC1 2, CF 3 CBrFCBrF 2, CClF 2 CClFCF 2 CCl 3, Cl (CF 2 CFCl) 2 Cl, Cl (CF 2 CFCl ) Fluorocarbon solvents such as ₂ CF ₂ CCl ₃ and Cl (CF ₂ CFCl) ₃ Cl; Fluorocarbon solvents such as Fluorinate (manufactured by 3M) and Afludo (manufactured by Asahi Glass); dimethyl silicone, phenyl silicone, alkyl Modified Siri And silicone solvents such as corn and polyether silicone. These solvents can be used alone or in combination of two or more.

  In order to suppress a rapid reaction, the water added in the method (a) and the catalyst A component added in the method (a) are preferably diluted with an organic solvent or the like.

  The organic thin film forming solution can be obtained from the silane-based surfactant and the catalyst A component or the silane-based surfactant and the catalyst B component. More specifically, by stirring the mixture of the silane surfactant, organic solvent, catalyst A component, and optionally water, or the silane surfactant, organic solvent, catalyst B component, and optionally A solution for forming an organic thin film can be obtained by stirring the water mixture.

  The amount of the catalyst A component and the catalyst B component used for the preparation of the organic thin film forming solution is not particularly limited as long as it does not affect the physical properties of the monomolecular organic thin film to be formed. It is usually 0.001 to 1 mol, preferably 0.001 to 0.2 mol in terms of moles in terms of oxide with respect to 1 mol.

  More specifically, the organic thin film forming solution includes (a) a method in which water is added to the organic solvent solution of the catalyst B component and the silane surfactant, and (b) a mixture of the silane surfactant and water. Examples thereof include a method of adding the catalyst B component to the solution. In order to suppress a rapid reaction, the water added in the method (a) and the catalyst B component added in the method (b) are preferably diluted with an organic solvent or the like.

  As the organic solvent used for the preparation of the organic thin film forming solution, a hydrocarbon solvent, a fluorocarbon solvent, and a silicone solvent are preferable, and those having a boiling point of 100 to 250 ° C. are more preferable. Specifically, the same hydrocarbon solvents, fluorocarbon solvents, and silicone solvents listed as those that can be used for the preparation of the catalyst A component and the catalyst B component can be used.

  The amount of water used for the preparation of the organic thin film forming solution can be appropriately determined according to the type of the silane-based surfactant used, the catalyst A component or the catalyst B component, the substrate to be applied, and the like. If the amount of water used is too large, the silane-based surfactants condense with each other, and chemical adsorption to the substrate surface may be hindered, so that a monomolecular film may not be formed.

  The stirring temperature of the mixture of the silane-based surfactant, organic solvent, catalyst A component, catalyst B component and water is usually −100 ° C. to + 100 ° C., preferably −20 ° C. to + 50 ° C. The stirring time is usually several minutes to several hours. In this case, it is also preferable to perform ultrasonic treatment in order to obtain a uniform solution for forming an organic thin film.

  In the present invention, it is preferable to use an organic thin film forming solution that has been adjusted or maintained so that its moisture content is within a predetermined range. Moisture content in the organic thin film forming solution impairs chemisorption on the substrate surface, cannot produce a fine monomolecular film, loses the amount of silane-based surfactant that can be used effectively, or An amount in a range that does not cause problems such as catalyst deactivation is preferred. Further, when the solution is brought into contact with the substrate by the dipping method, a dense and homogeneous organic thin film is formed once on the front surface of the substrate in contact with the solution within 10 minutes, preferably within 5 minutes. Therefore, it is preferable to have a moisture content that is sufficient to accelerate and activate the formation of the substrate surface or film.

  Specifically, the water content of the organic thin film forming solution is preferably 50 ppm or more, more preferably in the range of the saturated water content from 50 ppm to the organic solvent (more specifically, in the range of 50 to 1000 ppm).

  As a method for adjusting or maintaining the water content of the organic thin film forming solution within a predetermined range, (i) a method of providing a water layer in contact with the organic thin film forming solution, <ii) Examples thereof include a method in which a water-holding substance containing moisture is allowed to coexist, and (iii) a method in which a gas containing moisture is blown.

  Examples of the method for forming the organic thin film on the insulating film include a method in which the surface of the insulating film is brought into contact with the organic thin film forming solution obtained as described above.

  As a method of bringing the surface of the insulating film into contact with the organic thin film forming solution, a method in which the substrate on which the insulating film is formed is immersed in the organic thin film forming solution, or the organic thin film forming solution is applied to the insulating film surface by a known method. And a method of spraying a solution for forming an organic thin film on the insulating film. Especially, since the organic thin film which has uniform film quality can be formed into a film efficiently, the method of immersing the board | substrate with which the insulating film was formed in the solution for organic thin film formation is preferable. The immersion time is preferably 5 minutes or longer, and preferably within 10 minutes. And it is more preferable to ultrasonically clean after contact, such as immersion, using a hydrocarbon solvent solution or the like.

  After bringing the surface of the insulating film into contact with the organic thin film forming solution, it is preferable to provide a cleaning step in order to remove excess reagents, impurities, etc. adhering to the film surface. By providing the cleaning step, the film thickness can be controlled more. The cleaning method is not particularly limited as long as it can remove the deposits on the surface, but as described above, ultrasonic cleaning after immersion is more preferable using a hydrocarbon solvent solution or the like.

  After the organic thin film is formed or washed after forming the organic thin film, the substrate is preferably heated in order to stabilize the formed organic thin film layer. The heating temperature can be appropriately selected depending on the type of substrate used, the type of transparent conductive film, the stability of the formed organic thin film, and the like.

  When an insulating film is brought into contact with the organic thin film forming solution, the silane-based surfactant in the solution is adsorbed on the surface of the insulating film to form an organic thin film. Although the details of the mechanism by which the silane-based surfactant is adsorbed on the surface of the insulating film are not clear, it can be considered as follows. That is, in the organic thin film forming solution, the hydrolyzable group of the silane surfactant is in a state of being hydrolyzed by water. The silane-based surfactant in this state reacts with active hydrogen on the surface of the insulating film to form a thin film that forms a strong chemical bond with the surface of the insulating film. This thin film is formed by reacting with the active hydrogen of the insulating film and becomes a monomolecular film.

  Although the film thickness of the organic thin film depends on the alkyl chain length of the forming molecule, it is usually preferably 0.2 to 10 nm, particularly preferably 0.5 to 3 nm.

  By using the organic thin film forming solution, an organic thin film layer that is oil-repellent and water-repellent before light irradiation can be formed on the surface of the insulating film. More specifically, the contact angle of water before light irradiation is preferably 80 ° or more, more preferably 85 ° or more, still more preferably 90 ° or more, particularly preferably 100 ° or more, and the contact angle of toluene. It is possible to form an organic thin film having an excellent wear resistance of 20 ° or more.

Next, the organic semiconductor device manufacturing substrate 10 of the present invention shown in FIG. 1 can be obtained by removing the organic thin film from the region where the semiconductor film outside the gate electrode projection region is formed.
The method for removing the organic thin film from the region where the semiconductor film outside the gate electrode projection region is formed is not particularly limited, but the following methods (α) to (γ) are preferable from the viewpoint of work efficiency.

(Α) A method of removing an organic thin film from a region where a semiconductor film is formed outside a gate electrode projection region by irradiating a substrate having a structure shown in FIG.
First, a positive photoresist (not shown) is applied on the substrate 1 on which the gate electrode 2, the insulating film 3, and the organic thin film 4 are laminated, and ultraviolet rays are passed through a photomask well aligned with the substrate. Irradiate light to expose the photoresist. As a photomask to be used, for example, a metal film pattern made of Cr or the like is formed on the surface so as to shield the inside of the gate electrode projection region and transmit the portion where the organic semiconductor film is formed outside the gate electrode projection region. A photomask made of a quartz substrate can be used.

  Next, this is developed and baked to form a photoresist pattern which is disposed in the gate electrode projection region and not disposed in the organic semiconductor film formation portion outside the gate electrode projection region. Using this photoresist pattern as a mask, the organic thin film 4 was etched away by oxygen plasma treatment, and then the photoresist was removed, whereby the organic thin film 4 was selectively formed in the gate electrode projection region on the surface of the insulating film 3. The organic semiconductor device manufacturing substrate 10 of the present invention can be obtained.

(Β) Method Using Photolithographic Technology Also, in this case, as shown in FIG. 3, a plate having a photocatalyst layer formed from a composition for forming a photocatalyst layer containing at least titanium oxide on one surface side The transparent support 9 is overlapped with the substrate with the photocatalyst layer side facing the organic thin film 4 side, or the photocatalyst layer side is directed to the substrate side on which the organic thin film is formed and spaced apart from the substrate. Oppositely, active energy rays such as ultraviolet rays are irradiated from the other surface side (the upper side in the figure) of the support 9 to generate active species by a photocatalytic reaction. The organic semiconductor device of the present invention in which the organic thin film 4 is selectively formed in the gate electrode projection region on the surface of the insulating film 3 by decomposing and removing only the irradiated portion of the organic thin film 4 after modification with a predetermined pattern. Manufacturing substrate 1 It is possible to obtain. According to this method, the organic semiconductor device manufacturing substrate 10 of the present invention can be obtained simply and efficiently without using a photoresist.

(Γ) A method of removing an organic thin film from a region where a semiconductor film is formed outside a gate electrode projection region by irradiating light onto the substrate having the structure shown in FIG. (See FIG. 4).
First, a photoresist (not shown) is exposed from the back surface of the substrate using the gate electrode 2 as a photomask. Next, the organic thin film 4 is removed by etching using the photoresist processed into the same shape as the gate electrode as a mask, and then the organic thin film 4 is selected as the gate electrode projection region on the surface of the insulating film 3 by removing the photoresist. Thus, the organic semiconductor device manufacturing substrate 10 of the present invention can be obtained.

In the present invention, the following lift-off method can also be employed as another method.
First, after forming a photoresist in the gate electrode projection region on the surface of the insulating film 3, an organic thin film 4 is formed thereon. Here, an example is shown in which a photoresist is formed by a backside exposure method. In this case, a negative photoresist is used, and a photoresist outside the gate electrode projection region on the surface of the insulating film 3 is formed. When the photoresist is removed after the organic thin film 4 is formed thereon, the organic thin film 4 formed on the photoresist surface is removed (lifted off) together, and the organic thin film 4 becomes the gate electrode projection region on the surface of the insulating film 3. Thus, the organic semiconductor device manufacturing substrate 10 of the present invention selectively formed can be obtained.

  As described above, the organic semiconductor device manufacturing substrate 10 of the present invention can be manufactured. The obtained substrate 10 for manufacturing an organic semiconductor device has an organic thin film 4 that can be formed uniformly, with high quality and efficiency in the gate electrode projection region on the surface of the insulating film 3, so that a high orientation order is provided thereon. An organic semiconductor film having the same can be formed.

2) Organic semiconductor device and manufacturing method thereof The organic semiconductor device according to the present invention includes a gate electrode, a gate insulating film, a source electrode, a drain electrode, an organic semiconductor film, and a protective film stacked on a substrate. In the above, the semiconductor film is composed of an assembly of organic semiconductor molecules, and an interface portion between the semiconductor film and the insulating film formed in the gate electrode projection region on the surface of the insulating film has the formula (1): R _n − Si-X _4-n (wherein, R is an optionally substituted C1-20 hydrocarbon group, an optionally substituted C1-20 halogenated hydrocarbon group, a linking group) Represents a C1-20 hydrocarbon group containing 1 or a C1-20 halogenated hydrocarbon group containing a linking group, X represents a hydroxyl group, a halogen atom, a C1-6 alkoxy group or an acyloxy group, and n represents 1 to 1 Represents an integer of 3 Silane-based surfactant represented by.), And characterized by having an organic thin film formed from an organic thin film forming solution containing a catalyst capable of interacting with the silane-based surfactant.

  FIG. 5 shows a sectional view of the layer structure of the organic semiconductor device 20 of the present invention. In FIG. 5, 1 is a substrate, 2 is a gate electrode, 3 is an insulating film, 4 is an organic thin film, 5 is a drain electrode, 6 is a source electrode, 7 is an organic semiconductor film, and 8 is a protective film.

  The organic semiconductor device shown in FIG. 5 uses the organic semiconductor device manufacturing substrate shown in FIG. 1, and uses a drain electrode 5 and a source electrode 6 (hereinafter, also referred to as “drain / source electrodes 5 and 6”), organic. It can be manufactured by forming the semiconductor film 7 and the protective film 8.

  First, the drain / source electrodes 5 and 6 and the organic semiconductor film 7 are formed using the organic semiconductor device manufacturing substrate shown in FIG. In this case, the organic semiconductor film 7 can be formed after the drain / source electrodes 5 and 6 are formed, or the drain / source electrodes 5 and 6 can be formed after the organic semiconductor film 7 is formed.

  Among these, the method of forming the drain / source electrodes 5 and 6 first has the following advantages. The organic thin film 4 selectively disposed in the gate electrode projection region on the surface of the insulating film 3 selectively improves only the alignment order of the organic semiconductor film 7 formed on the region, thereby increasing the light leakage current. In addition to improving the switching performance in the dark state, the drain electrode 5 and the source electrode 6 are arranged in a self-aligned manner with respect to the gate electrode. That is, the conductive ink does not permeate into the gate electrode projection region due to the lyophobic action of the organic thin film 4, and a drain / source electrode whose end is aligned with the gate electrode can be formed.

  In general, the electrodes formed by the coating process have low pattern and positional accuracy. Therefore, when the electrodes are formed so that they are not short-circuited, the electrode spacing and channel length are as large as about 30 μm, and sufficient current can be obtained. I couldn't. On the other hand, according to the present invention, the channel length is determined by the width of the organic thin film 4 arranged in the gate electrode projection region, that is, the width of the gate electrode 2. Therefore, if the gate electrode 2 is formed by a photolithography method with high positional accuracy, the drain / source electrodes 5 and 6 having a gate electrode width of about 3 μm, that is, a channel length can be formed by a coating process.

  Further, when forming the drain / source electrodes 5 and 6 after forming the organic semiconductor film 7, a photoresist is formed so as to cover the organic semiconductor film 7, and then patterning is performed, so that the drain electrode 5 and the source electrode are formed. The drain / source electrodes 5 and 6 can be formed by mask vapor deposition of the electrode 6 material.

  As a material for forming the drain / source electrode, since most organic semiconductors are p-type semiconductors in which carriers for transporting charges are holes, a metal having a large work function is used to make ohmic contact with the organic semiconductor film. desirable. Specific examples include gold and platinum, but are not limited to these materials. In addition, when a dopant is densely doped on the surface of the semiconductor layer, carriers can tunnel between the metal and the semiconductor, and it does not depend on the material of the metal. Can also be used as a material for the source and drain electrodes.

The organic semiconductor film 7 can be formed by forming a thin film of an organic semiconductor material on the organic thin film 4 of the substrate 10 for manufacturing an organic semiconductor device of the present invention shown in FIG. When the layer of the organic semiconductor material is formed on the organic thin film 4, the organic semiconductor material is crystallized and oriented by the organic thin film, and the organic semiconductor film 7 having a high orientation order is formed. Note that even if a thin film of an organic semiconductor material is formed in a portion other than on the organic thin film 4 due to a film formation error, the organic semiconductor material does not crystallize and orientate, so that an organic semiconductor film having properties as a semiconductor is not formed.
The orientation order of the organic semiconductor film 7 can be confirmed by measuring the surface shape of the organic semiconductor film 7 using an atomic force microscope (AFM) or an X-ray diffraction measuring apparatus.

  The organic semiconductor material to be used is not particularly limited, and examples thereof include π electron conjugated aromatic compounds, chain compounds, organic pigments, and organic silicon compounds. More specifically, pentacene, tetracene, thiophen oligomer derivatives, phenylene derivatives, phthalocyanine compounds, polyacetylene derivatives, polythiophene derivatives, cyanine dyes, and the like.

  A method for forming a thin film using a semiconductor organic material as a raw material is not particularly limited, and examples thereof include a spin coating method, a casting method, a pulling method, a dipping method, and a vacuum deposition method.

  Finally, a protective film 8 is formed on the entire substrate surface. The protective film 8 can be formed by using the same material as the insulating film 3 and by the same film forming method. The thickness of the protective film 8 is not particularly limited, but is usually about 100 to 1000 nm.

As described above, the organic semiconductor device 20 of the present invention having the structure shown in FIG. 5 can be obtained.
Since the organic semiconductor device of the present invention has an organic semiconductor film having a high orientation order, it has excellent characteristics as a transistor.
In other words, since the organic semiconductor device of the present invention improves the switching performance without increasing the light leakage current as described above, the liquid crystal display device can be driven without malfunction even with high luminance backlight light. can do.

It is layer structure sectional drawing of an example of the board | substrate for organic-semiconductor device manufacture of this invention. It is process sectional drawing showing the manufacturing process of the board | substrate for organic-semiconductor device manufacture of this invention. It is a figure explaining the selective formation method of the organic thin film which is one embodiment of this invention. It is a figure explaining the selective formation method of the organic thin film which is one embodiment of this invention. It is layer structure sectional drawing of an example of the organic-semiconductor device of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Gate electrode, 3 ... Insulating film (gate insulating film), 4 ... Organic thin film ... 5 ... Drain electrode, 6 ... Source electrode, 7 ... Organic semiconductor film, 8 ... Protective film, 9 ... Support body, DESCRIPTION OF SYMBOLS 10 ... Substrate for organic semiconductor device manufacture, 20 ... Organic semiconductor device

Claims (21)

A substrate for manufacturing an organic semiconductor device, comprising: a substrate; a gate electrode formed on the substrate; a gate insulating film formed on the gate electrode; and an organic thin film formed on the gate insulating film. , the organic thin film is of the formula _{(1): R n -Si-} X 4-n ( wherein, R have hydrocarbon group C1~20 which may have a substituent, a substituent A C1-20 halogenated hydrocarbon group, a C1-20 hydrocarbon group containing a linking group, or a C1-20 halogenated hydrocarbon group containing a linking group, wherein X is a hydroxyl group, a halogen atom, C1 6 represents an alkoxy group or an acyloxy group, and n represents an integer of 1 to 3), and a solution for forming an organic thin film comprising a catalyst capable of interacting with the silane surfactant. It is characterized by being an organic thin film formed from Organic semiconductor device manufacturing substrate.   The catalyst is a metal oxide; a metal hydroxide; a metal alkoxide; a chelated or coordinated metal compound; a metal alkoxide partial hydrolysis product; a metal alkoxide more than twice the equivalent of the metal alkoxide. The substrate for manufacturing an organic semiconductor device according to claim 1, which is at least one selected from a hydrolysis product obtained by treating with water, an organic acid, a silanol condensation catalyst, and an acid catalyst.   The catalyst comprises: (a) a metal oxide; a metal hydroxide; a metal alkoxide; a chelated or coordinated metal compound; a metal alkoxide partial hydrolysis product; A hydrolysis product obtained by treatment with water equivalent to a double equivalent or more; an organic acid; a silanol condensation catalyst; and an acid catalyst; and (b) a composition containing the silane-based surfactant. The substrate for manufacturing an organic semiconductor device according to claim 1, wherein the substrate is for manufacturing an organic semiconductor device.   4. The substrate for manufacturing an organic semiconductor device according to claim 2, wherein the metal alkoxide is a titanium alkoxide.   The substrate for manufacturing an organic semiconductor device according to claim 4, wherein the titanium alkoxide is titanium tetraisopropoxide.   6. The organic semiconductor device manufacturing substrate according to claim 1, wherein the organic thin film forming solution is a hydrocarbon solvent solution.   The substrate for manufacturing an organic semiconductor device according to claim 6, wherein the hydrocarbon solvent is toluene.   The substrate for manufacturing an organic semiconductor device according to any one of claims 1 to 7, wherein the amount of water in the solution for forming an organic thin film is within a range of a saturated water content from 50 ppm to an organic solvent. In an organic semiconductor device composed of a gate electrode, a gate insulating film, a source electrode, a drain electrode, a semiconductor film, and a protective film stacked on a substrate, the semiconductor film is composed of an assembly of organic semiconductor molecules, the interface portions of the semiconductor film and the insulating film formed on the gate electrode projection area of the insulating film surface, wherein _{(1): R n -Si-} X 4-n ( wherein, R has a substituent The C1-20 hydrocarbon group which may have a substituent, the C1-20 halogenated hydrocarbon group which may have a substituent, the C1-20 hydrocarbon group containing a connecting group, or the C1-20 containing a connecting group X represents a hydroxyl group, a halogen atom, a C1-6 alkoxy group or an acyloxy group, and n represents an integer of 1 to 3), and Mutual with silane surfactant An organic semiconductor device comprising an organic thin film formed from an organic thin film forming solution containing a catalyst capable of acting.   The organic semiconductor device according to claim 9, wherein the organic thin film is not interposed at an interface between the semiconductor film and the gate insulating film formed outside the region.   The alignment order of organic semiconductor molecules in the semiconductor film portion formed in the gate electrode projection region on the insulating film surface is higher than the alignment order in the semiconductor film portion formed outside the region. 9. The organic semiconductor device according to 9 or 10.   The catalyst is a metal oxide; a metal hydroxide; a metal alkoxide; a chelated or coordinated metal compound; a metal alkoxide partial hydrolysis product; a metal alkoxide more than twice the equivalent of the metal alkoxide. The organic semiconductor according to any one of claims 9 to 11, which is at least one kind selected from a hydrolysis product obtained by treating with water, an organic acid, a silanol condensation catalyst, and an acid catalyst. apparatus.   The catalyst comprises: (a) a metal oxide; a metal hydroxide; a metal alkoxide; a chelated or coordinated metal compound; a metal alkoxide partial hydrolysis product; A hydrolysis product obtained by treatment with water equivalent to a double equivalent or more; an organic acid; a silanol condensation catalyst; and an acid catalyst; and (b) a composition containing the silane-based surfactant. The organic semiconductor device according to claim 9, wherein the organic semiconductor device is provided.   14. The organic semiconductor device according to claim 12, wherein the metal alkoxide is a titanium alkoxide.   The organic semiconductor device according to claim 14, wherein the titanium alkoxide is titanium tetraisopropoxide.   16. The organic semiconductor device according to claim 9, wherein the organic thin film forming solution is a hydrocarbon solvent solution.   The organic semiconductor device according to claim 16, wherein the hydrocarbon solvent is toluene.   The organic semiconductor device according to any one of claims 9 to 17, wherein the water content in the organic thin film forming solution is within a range of a saturated water content from 50 ppm to an organic solvent.   The organic thin film forming substrate according to claim 1 is irradiated with light from the substrate surface through a photomask to remove the organic thin film from a region where the semiconductor film outside the gate electrode projection region is formed. A method for manufacturing an organic semiconductor device, comprising:   The organic thin film is formed from the region where the semiconductor film outside the gate electrode projection region is formed by irradiating the organic semiconductor device forming substrate according to any one of claims 1 to 8 with light from the back surface of the substrate using the gate electrode as a photomask. A method for producing an organic semiconductor device, comprising removing the organic semiconductor device. A plate-like transparent support having a photocatalyst layer formed of a composition for forming a photocatalyst layer containing at least titanium oxide on one surface side is overlaid on the substrate with the photocatalyst layer side facing the organic thin film side, Alternatively, the photocatalyst layer side is opposed to the substrate at a predetermined interval toward the substrate side on which the organic thin film is formed, and activated by photocatalytic reaction by irradiating active energy rays from the other surface side of the support. A method for producing an organic semiconductor device, comprising generating seeds and modifying the surface of the organic thin film in a predetermined pattern with the active species, and then decomposing and removing only irradiated portions of the organic thin film.

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