JP2009081309A - Organic semiconductor composition and organic electronic device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide, with a comparatively simplified method, an organic semiconductor material showing an excellent semiconductor characteristic which may be used to form a thin film having uniform film quality with a solution process. <P>SOLUTION: The organic semiconductor composition is formed of a composition 1 including a π-conjugate compound A and at least a kind of compound B in which a part of the hydrogen atoms or substituents of the π-conjugate compound A is replaced by a soluble group R or hydrogen atom (at least one is R) as an organic semiconductor element, where a difference between the total sum of Hammet constants of soluble group R of the compound B and the total sum of Hammet constants of the substituent to be replaced of the compund A is equal to or within 1.0 and a solvent in which the boiling point of at least a kind is 40°C or higher and 120°C or lower is included at a mass ratio of 1/20 times or more but under 1,000 times for the organic semiconductor element. This organic semiconductor composition is expressed by the following general expression 1. (In the expression, R indicates the substituent; n indicates a natural number; when a plurality of soluble groups R are provided, these may be the same or different and the sign + indicates a uniform mixture of these groups). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic semiconductor material comprising a composition of a π-conjugated compound and a compound in which a solubilizing group is bonded to the π-conjugated compound, a method for producing the same, a film comprising the organic semiconductor material, and an organic electronic device (particularly organic Transistor, organic photoelectric conversion element).

  In the ubiquitous information society, there is a need for information terminals that can be used anytime and anywhere. For this reason, flexible, lightweight, and inexpensive electronic devices are desired, but conventional electronic devices using inorganic materials such as silicon cannot sufficiently meet these demands. In recent years, therefore, research on organic electronic devices using organic materials that can meet these demands as semiconductors has been actively conducted. In particular, an organic semiconductor material that can be applied and dried as a solution on a substrate, that is, a film that can be formed by a so-called solution process, does not require a high-temperature process and enables the production of a large-area device at low cost. Therefore, it is highly expected (Non-Patent Documents 1 and 2).

However, organic semiconductor materials that have been found so far have relatively high performance, as represented by pentacene and fullerene C ₆₀ , and have a large π-conjugated system, so that the solubility in a solvent is very high. Most were low and poor in solution process suitability. For this reason, a high-cost so-called vacuum process such as a vacuum deposition method has to be used for film formation. On the other hand, introduction of a substituent to the organic semiconductor skeleton for the purpose of imparting solubility and suitability for solution process often inhibits the packing property of molecules in the film and leads to a decrease in carrier transport property. For this reason, there is a strong demand for the development of organic semiconductor materials that can be formed by a solution process and exhibit relatively good characteristics.

  Many of the organic semiconductor materials known so far are p-type materials having holes as charge transport carriers. As a p-type material, P3HT (poly (3-hexylthiophene)) that can be coated and formed is known, and since this material exhibits relatively good characteristics, it is widely used as a p-type material that can be coated and formed. ing.

On the other hand, in the n-type material in which the charge transport carrier is an electron, only a small part of the material can be subjected to solution process film formation. The most frequently used material is fullerene derivative PCBM ([6,6] -phenyl-C61-butyric acid methyl ester). However, in order to operate this as an electronic device, sealing was necessary to prevent deterioration in the atmosphere, and the stability in the atmosphere was not satisfactory. In addition, hexadecafluorocopper phthalocyanine (F ₁₆ CuPc) is known as an n-type material that hardly deteriorates in the air, but has a problem that it has low solubility in a solvent and is not suitable for film formation by a solution process. (Non-Patent Documents 1 and 2).

  Accordingly, there is a demand for the development of an organic semiconductor material that is suitable for film formation in a solution process such as a coating method and exhibits good characteristics, in particular, an n-type material that has little deterioration in characteristics even in the atmosphere.

Chemical Reviews, 2007, 107, 1296-1323. “Organic Field-Effect Transistors” (2007, CRC Press), pages 159-228.

  The present invention has been made in view of the above-mentioned background, and the object thereof is to form a thin film having a uniform film quality by a solution process, and to make an organic semiconductor material exhibiting good semiconductor characteristics relatively simple. It is to be provided by a method.

The object of the present invention is to provide an organic semiconductor material comprising a composition of a π-conjugated compound having a specific structure described in the following (1) to (11), a film comprising the organic semiconductor material, and various organic electronic devices (Especially organic transistors, organic photoelectric conversion elements).
(1) π-conjugated compound A and at least one kind of compound B in which a part of the hydrogen atom or substituent of π-conjugated compound A is replaced with solubilizing group R or hydrogen atom (at least one is R) are organic The composition 1 is included as a semiconductor component, and the difference between the sum of the Hammet constants of the solubilizing group R of the compound B and the sum of the Hammet constants of the substituents substituted for the compound A is within 1.0, and at least one kind An organic semiconductor composition comprising a solvent having a boiling point of 40 ° C. or higher and 120 ° C. or lower in a mass ratio with respect to the organic semiconductor component of 1/20 times or more and less than 1000 times.

(In the formula, R represents a substituent, and n represents a natural number. When there are a plurality of Rs, the plurality of Rs may be the same or different from each other. + Represents a homogeneous mixture of the two (the same applies hereinafter). ).)
(2) The organic semiconductor composition according to (1), wherein the content of compound A and at least one compound B in the organic semiconductor component is 10% by mass or more.
(3) The organic semiconductor according to (1) or (2), wherein the composition contains the following π-conjugated compound A1 and compound B1 and is represented by the following general formula 2 comprising phthalocyanine or an analog thereof: Composition.

(In the formula, M represents a metal atom or a hydrogen atom (when M is a hydrogen atom, two hydrogen atoms are bonded to nitrogen atoms of N ¹ and N ² , respectively.) Q represents an aromatic hydrocarbon ring or aromatic group. Represents a group of atoms necessary to form a group heterocycle, a plurality of Qs may be the same or different, R represents a substituent, n represents a natural number, and when R is a plurality, a plurality of R May be the same or different.)
(4) The organic semiconductor composition according to any one of (1) to (3), wherein at least one of the organic semiconductor components is an n-type organic semiconductor.
(5) The organic semiconductor composition according to any one of (1) to (4), wherein the composition contains the following π-conjugated compound A2 and compound B2 and is represented by the following (general formula 3): .

(In the formula, M represents a metal atom or a hydrogen atom (in the case of a hydrogen atom, bonded to a nitrogen atom of an isoindole ring and a nitrogen atom of an isoindoline ring), m represents a natural number, R represents a substituent, n represents a natural number. When there are a plurality of R, the plurality of R may be the same or different.
(6) The organic semiconductor composition according to any one of (1) to (5), wherein the solubilizing group R is —SO ₂ R ′ or —SO ₂ NR ′ ₂ (R ′ represents a substituent).
(7) The manufacturing method of the organic-semiconductor composition in any one of (1)-(6) using using an organic-semiconductor component by mixing and making it react with 2 or more types of phthalonitrile or its derivative (s).
(8) A film formed using the organic semiconductor composition according to any one of (1) to (6).
(9) The film according to (8), wherein the film forming method is a solution process.
(10) An organic electronic device using the organic semiconductor composition according to any one of (1) to (6).
(11) An organic transistor using the organic semiconductor composition according to any one of (1) to (6).
(12) An organic photoelectric conversion device using the organic semiconductor composition according to any one of (1) to (6).

  According to the present invention, a thin film having a uniform film quality can be formed by a solution process, and an organic semiconductor material exhibiting good semiconductor characteristics is provided by a relatively simple method. High-performance organic electronic devices (organic transistors, organic photoelectric conversion elements, etc.) can be obtained.

  The present invention is described in detail below.

  The π-conjugated compound A of the present invention may have any structure as long as it has an aromatic hydrocarbon ring or an aromatic heterocycle. For example, “Organic Field-Effect Transistors” (2007, CRC Press) pages 159-228. And other known organic semiconductor molecules. Preferably an aromatic hydrocarbon ring or aromatic such as benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, furan ring, thiophene ring It is a structure having a hetero ring, and more preferably, two or more of these aromatic hydrocarbon rings or aromatic hetero rings are condensed and / or covalently linked, and the aromatic ring It is preferable that the π electron which each hydrocarbon ring or aromatic hetero ring has is widely delocalized. The number of condensed aromatic rings and / or covalently linked aromatic hydrocarbon rings or aromatic heterocycles is preferably 1-20, more preferably 2-12.

  Specific examples of the π-conjugated compound A in the present invention include condensed polycyclic compounds such as anthracene, tetracene, pentacene, triphenylene, hexabenzocoronene, fullerene, aromatic heterocyclic oligomers such as quarterthiophene and sexithiophene, and phthalocyanines. And porphyrins.

  The π-conjugated compound A of the present invention alone preferably has low solubility in a solvent. Specifically, among various general-purpose solvents as a solvent, when the solvent having the highest solubility is used, the compound is heated to reflux to the boiling point. A material having a solubility of 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, after cooling to room temperature (25 ° C.). Here, the general-purpose solvent may be any, for example, a hydrocarbon solvent such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, 1,2-dichlorobenzene, such as acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone and cyclohexanone, for example, halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, such as ethyl acetate, acetic acid Ester solvents such as butyl and amyl acetate, such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, Alcohol solvents such as tylene glycol, for example, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1- Polar solvents such as methyl-2-imidazolidinone and dimethyl sulfoxide), water and the like. These solvents may be used alone or in combination.

In the present invention, an organic semiconductor material comprising a composition containing at least one kind of a π-conjugated compound A and a compound B having a solubilizing group R with respect to a part of the structure of the compound A in order to impart solution process suitability. (Hereinafter referred to as “the organic semiconductor composition of the present invention”).
In the present invention, the compound B has improved solubility in a solvent by introducing the solubilizing group R. The solubility of Compound B is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more in the solvent exhibiting the highest solubility.

  The number of compound B may be not limited to one, and the mixing ratio can be appropriately changed according to the purpose of use. As the number of types of compound B in the organic semiconductor composition increases, the solution process suitability tends to improve, but the semiconductor characteristics tend to deteriorate, and an appropriate number of types can be selected according to the purpose. Compound B is preferably one to twenty, more preferably one to ten.

  In the present invention, the organic semiconductor composition may be solid or liquid, but is preferably a solution or dispersion of an organic semiconductor component. In addition, by incorporating a very small amount of a solvent having a boiling point of 40 ° C. or higher and 120 ° C. or lower with respect to the organic semiconductor component, molecular integration of the organic semiconductor component during application / drying of the organic semiconductor composition can be promoted. The solvent having a boiling point of 40 ° C. or more and 120 ° C. or less may be any solvent as long as the boiling point falls within this range. Examples thereof include hexane (boiling point 69 ° C.), octane (126 ° C.), benzene (80 ° C), toluene (111 ° C), acetone (56 ° C), methyl ethyl ketone (80 ° C), methyl isobutyl ketone (116 ° C), dichloromethane (40 ° C), chloroform (62 ° C), tetrachloromethane (77 ° C), dichloroethane (84 ° C), trichloroethane (87 ° C), ethyl acetate (77 ° C), methanol (65 ° C), ethanol (78 ° C), n-propanol (97 ° C), isopropanol (82 ° C), n-butanol (117 ° C) , Diisopropyl ether (69 ° C.), tetrahydrofuran (66 ° C.), 1,4-dioxane (101 ° C.) Water (100 ° C.), and the like pyridine (115 ° C.). The boiling point is preferably 60 ° C. or higher and 120 ° C. or lower, more preferably 80 ° C. or higher and 120 ° C. or lower, and particularly preferably toluene, pyridine, benzene or water. If the amount of the solvent is too large, the organic semiconductor component will be deposited before coating and drying, and a high-quality thin film cannot be obtained. Therefore, the organic semiconductor component contains at least 1/1000 times and less than 100,000 times in mass ratio. It is preferable to contain 1/100 times or more and less than 10,000 times, and more preferably 1/20 or more times and less than 1000 times.

The proportions of Compound A and Compound B in the composition are not particularly limited, but it is preferable that both Compound A and at least one compound B are contained in an amount of 0.001% by mass or more. More preferably, it is contained in an amount of 01% by mass or more, and more preferably 0.02% by mass or more. The upper limit can be determined within the range in which the compound A or B does not precipitate as described above, but is preferably 10% by mass or less, more preferably 5% by mass or less.
In addition, the ratio of the amount of compound A and compound B used in the organic semiconductor composition is not particularly limited, but considering the use as an organic semiconductor material, compound B with respect to compound A is preferably used in a mass ratio. 1/100 to 100/1, more preferably 1/10 to 10/1.

  Energy levels of π-conjugated compound A and compound B contained for improving solubility (redox potential, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), ionization potential (Ip) and electron If the difference in affinity (which may be paraphrased as affinity (Ea) or the like) is large, it becomes a trap during carrier transport, so that the semiconductor characteristics are degraded. For this reason, the difference in energy level between compound A and compound B is preferably as small as possible. The oxidation-reduction potential of the compound can be determined by performing CV (cyclic voltammetry) measurement in an appropriate solvent. In addition, it is possible to measure Ip (eV) by performing atmospheric photoelectron spectroscopy on the solid film, and further, energy gaps Eg (eV) and Ea (calculated from the absorption long wavelength end of the solid film). ev) = Ea can be obtained from the relationship of Ip−Eg.

  The smaller the energy level difference between Compound A and Compound B, the better. The difference between Ip and Ea is preferably within 1.5 eV, more preferably within 1.0 eV, and more preferably 0.5 eV. More preferably, it is within.

It is known that there is a good correlation between the Hammet constant σ of the substituent bonded to the π-conjugated compound and the energy level (Inorg. Chim. Acta, 1993, 203, 171; J. Electroana. Chem. , 1999, 476, 148, etc.). Therefore, in order to reduce the difference in energy level between Compound A and Compound B, the sum of the Hammet constants Σσ B of the solubilizing group R of Compound _B and the sum of the Hammet constants of the substituents replaced by Compound A Σσ _A The difference (| Σσ _B −Σσ _A |) may be reduced. The difference in the sum of the Hammet constants is preferably as small as possible, preferably 1.5 or less, more preferably 1.0 or less, and particularly preferably 0.5 or less.

In the present invention, the Hammet constant σ is determined according to the literature Chem. Rev. 1991, 91, 165. The average value of the sigma _o and sigma _p according to _{(σ = (σ o + σ} p) / 2). For substituents not described in the paper, the Hammet constant of the substituent having the most similar structure is used.

  The solubilizing group R may be any substituent and can be selected from W described later. The number n of solubilizing groups R contained in one molecule is not particularly limited, and may be one or more. As R increases, solution process suitability tends to improve, but semiconductor properties tend to deteriorate, and an appropriate number can be selected according to the application. Preferably they are 1-10 pieces, More preferably, they are 1-5 pieces, More preferably, they are 1-3 pieces. When there are a plurality of R, the plurality of R may be the same or different.

  In the present invention, when a specific moiety represented by R is referred to as a “group”, the group R in the moiety may not be substituted per se, and one or more (up to the maximum possible number) Means that it may be further substituted with another substituent. For example, “alkyl group” means a substituted or unsubstituted alkyl group. That is, the substituent in the compound in the present invention may be further substituted.

When the substituent represented by R is W, any substituent may be used, and there is no particular limitation. For example, a halogen atom, an alkyl group (in addition to a linear or branched alkyl group, A cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkenyl group (including a straight-chain or branched alkenyl group, a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (hetero May be referred to as a cyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxy Carbonyloxy group, amino group (including anilino group), ammoni Group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group , Sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyl Oxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—O Examples include SO ₃ H) and other substituents that impart solvent solubility to the known compound B.

More specifically, W represents the following (1) to (48).
(1) Halogen atom For example, fluorine atom, chlorine atom, bromine atom, iodine atom

(2) Alkyl group represents a linear, branched or cyclic substituted or unsubstituted alkyl group. They also include (2-a) to (2-e).

(2-a) alkyl group Preferably an alkyl group having 1 to 30 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl) )

(2-b) cycloalkyl group Preferably, the substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms (for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl).

(2-c) Bicycloalkyl group Preferably, the substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms (for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] Octane-3-yl)

(2-d) Tricycloalkyl group Preferably, it is a substituted or unsubstituted tricycloalkyl group having 7 to 30 carbon atoms (for example, 1-adamantyl).

(2-e) A polycyclic cycloalkyl group having a larger ring structure In addition, an alkyl group (for example, an alkyl group of an alkylthio group) in a substituent described below represents an alkyl group of such a concept, Group and alkynyl group.

(3) Alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They include (3-a) to (3-c).

(3-a) Alkenyl group Preferably it is a C2-C30 substituted or unsubstituted alkenyl group (for example, vinyl, allyl, prenyl, geranyl, oleyl).

(3-b) Cycloalkenyl group Preferably, the substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl)

(3-c) Bicycloalkenyl group A substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms (for example, bicyclo [2,2,1] hept-2-ene -1-yl, bicyclo [2,2,2] oct-2-en-4-yl)

(4) Alkynyl group Preferably, the substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms (for example, ethynyl, propargyl, trimethylsilylethynyl group)

(5) Aryl group Preferably, it is a C6-C30 substituted or unsubstituted aryl group (for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, ferrocenyl).

(6) Heterocyclic group Preferably, it is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably carbon. It is a 5- or 6-membered aromatic heterocyclic group of formula 3 to 50.
(For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl. In addition, a cationic heterocyclic group such as 1-methyl-2-pyridinio and 1-methyl-2-quinolinio may be used)

(7) Cyano group

(8) Hydroxy group

(9) Nitro group

(10) Carboxy group

(11) Alkoxy group

  Preferably, it is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms (for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy).

(12) Aryloxy group Preferably, the substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoyl) Aminophenoxy)

(13) Silyloxy group Preferably, the silyloxy group having 3 to 20 carbon atoms (for example, trimethylsilyloxy, t-butyldimethylsilyloxy)

(14) Heterocyclic oxy group Preferably, the substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy)

(15) Acyloxy group, preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms (for example, formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy)

(16) Carbamoyloxy group Preferably, the substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms (for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N- Di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy)

(17) Alkoxycarbonyloxy group Preferably, the substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms (for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy)

(18) Aryloxycarbonyloxy group Preferably, the substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms (for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyl) Oxy)

(19) Amino group Preferably, an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms (for example, amino, methylamino, dimethylamino, Anilino, N-methyl-anilino, diphenylamino)

(20) Ammonio group Preferably, an ammonio group, an ammonio group substituted with 1 to 30 carbon atoms or an unsubstituted alkyl, aryl, or heterocyclic ring (for example, trimethylammonio, triethylammonio, diphenylmethylammonio)

(21) Acylamino group Preferably, a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms (for example, formylamino, acetyl) Amino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino)

(22) Aminocarbonylamino group Preferably, the substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms (for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino) )

(23) Alkoxycarbonylamino group Preferably, the substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms (for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N- Methyl-methoxycarbonylamino)

(24) Aryloxycarbonylamino group Preferably, the substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms (for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) )

(25) Sulfamoylamino group Preferably, the substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms (for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino) Sulfonylamino)

(26) Alkyl or arylsulfonylamino group Preferably, the substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, or the substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms (for example, methylsulfonylamino, butylsulfonyl) Amino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino)

(27) Mercapto group

(28) Alkylthio group Preferably, it is a C1-C30 substituted or unsubstituted alkylthio group (for example, methylthio, ethylthio, n-hexadecylthio).

(29) Arylthio group Preferably, the substituted or unsubstituted arylthio having 6 to 30 carbon atoms (for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio)

(30) Heterocyclic thio group Preferably, the substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms (for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio)

(31) Sulfamoyl group Preferably, the substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms (for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl) N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl)

(32) Sulfo group

(33) an alkyl or arylsulfinyl group, preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms (for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl)

(34) an alkyl or arylsulfonyl group, preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl)

(35) Acyl group Preferably, it is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 4 to 30 carbon atoms. Heterocyclic carbonyl groups bonded to carbonyl groups at substituted carbon atoms (eg, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl )

(36) Aryloxycarbonyl group Preferably, it is a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms (for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl). )

(37) Alkoxycarbonyl group Preferably, the substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl)

(38) Carbamoyl group Preferably, the substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms (for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (Methylsulfonyl) carbamoyl)

(39) Aryl and heterocyclic azo group Preferably, the substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, or the substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (for example, phenylazo, p-chlorophenylazo , 5-ethylthio-1,3,4-thiadiazol-2-ylazo)

(40) Imido group, preferably N-succinimide, N-phthalimide

(41) Phosphino group Preferably, the substituted or unsubstituted phosphino group having 2 to 30 carbon atoms (for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino)

(42) Phosphinyl group Preferably, the substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms (for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl).

(43) Phosphinyloxy group Preferably, the substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms (for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy)

(44) Phosphinylamino group Preferably, the substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms (for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino)

(45) Phosphor group

(46) Silyl group Preferably, the substituted or unsubstituted silyl group having 3 to 30 carbon atoms (for example, trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl)

(47) Hydrazino group Preferably a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms (for example, trimethylhydrazino)

(48) Ureido group Preferably, the substituted or unsubstituted ureido group having 0 to 30 carbon atoms (for example, N, N-dimethylureido)
Of these substituents W, preferably (2), (3), (4), (5), (6), (11), (12), (13), (14), (15) , (16), (17), (18), (19), (20), (21), (22), (23), (24), (25), (26), (28), ( 29), (30), (31), (33), (34), (35), (36), (37), (38), (39), (41), (42), (43) , (44), (46), (47), (48).
The solubilization by the solubilizing group is also related to the solvent used for coating in the organic semiconductor composition. Examples of the solvent include the general-purpose solvents.
The solubilizing group is appropriately determined depending on the type of solvent used in the organic semiconductor composition in consideration of a predetermined solubility.

  Two Ws can also form a ring together. Examples of such a ring include an aromatic or non-aromatic hydrocarbon ring, a hetero ring, and a polycyclic fused ring formed by further combining these rings. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, Pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenant Examples include lysine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, and phenazine ring. Among these, preferred ring compounds are a benzene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, and a pyrazine ring. However, the aromatic ring is not preferable because it rarely improves the solubility of the phthalocyanine compound of the present invention in a solvent.

Among the above-described substituents W, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such substituents include a —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ — group (sulfonylsulfamoyl group). ). More specifically, alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), arylsulfonylamino A carbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

  The π-conjugated compound A and compound B used in the present invention are phthalocyanine and its analogs (compound A1 or B1) represented by the following chemical formula (Chemical Formula 2) from the viewpoint of semiconductor properties and compound stability. Is particularly preferred.

(In the formula, M represents a metal atom or a hydrogen atom (when M is a hydrogen atom, two hydrogen atoms are bonded to nitrogen atoms of N ¹ and N ² , respectively.) Q represents an aromatic hydrocarbon ring or aromatic group. Represents a group of atoms necessary to form a group heterocycle, a plurality of Qs may be the same or different, R represents a substituent, n represents a natural number, and when R is a plurality, a plurality of R May be the same or different, as indicated above, + indicates a mixture of both.)

  In the general formula 2, R is bonded to either the ring consisting of M or Q, but preferably bonded to the ring consisting of Q.

In General Formula 2, M represents a metal atom or two hydrogen atoms bonded to the nitrogen atom represented by N ¹ and N ² . When M represents a metal atom, any metal can be used as long as it forms a stable complex, and Li, Na, K, Be, Mg, Ca, Ba, Al, Si, Hg, Cr, Fe, Co, Ni, Cu, Zn, Ge, Pd, Cd, Sn, Pt, Pb, Sr, V, Mn, Ti, In, or Ga can be used. A substituent may be bonded to the metal atom, and the aforementioned W can be used as the substituent. The preferred _{M Mg, Ca, AlCl, SiCl} 2, Fe, Co, Ni, Cu, Zn, Pd, Sn, SnCl 2, Pt, Pb, V = O, Mn, Ti = O is used, more preferably Fe, Co, Ni, Cu, and Zn are used, and Cu and Zn are particularly preferably used. M is preferably a hydrogen atom. General formula 2 in the case where M is a hydrogen atom is represented by the following general formula 2 ′.

(In the formula, Q represents an atomic group necessary to form an aromatic hydrocarbon ring or an aromatic heterocycle. Plural Qs may be the same or different. R represents a substituent, and n represents a substituent. Represents a natural number. When there are a plurality of R, the plurality of R may be the same or different.

  In the general formula 2, the aromatic hydrocarbon ring or aromatic heterocycle consisting of Q may be any one, specifically, among those listed as W, the aromatic hydrocarbon ring and the aromatic heterocycle. Those mentioned in the item of the ring can be mentioned. A 5- to 7-membered ring is more preferable, a 5- or 6-membered ring is more preferable, and a 6-membered ring is particularly preferable. Although the hetero atom contained in the aromatic heterocycle formed by Q is not particularly limited, nitrogen, oxygen, sulfur, selenium, silicon, germanium or phosphorus is preferable, nitrogen, oxygen or sulfur is more preferable, and nitrogen is particularly preferable. The number of heteroatoms contained in one aromatic heterocycle formed by Q is not particularly limited, but is preferably 1 to 3.

Specific examples of the aromatic hydrocarbon ring or aromatic heterocycle formed by Q include benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring. Oxadiazole ring, thiazole ring, thiadiazole ring, furan ring, thiophene ring, selenophene ring, silole ring, germol ring, phosphole ring and the like. Preferred are benzene ring, pyridine ring, pyrazine ring, pyrrole ring, imidazole ring, triazole ring, oxazole ring, oxadiazole ring, thiazole ring, thiadiazole ring, furan ring, thiophene ring, selenophene ring, silole ring, and more preferred. Are a benzene ring, a pyridine ring, a pyrazine ring, and a thiophene ring.
The aromatic hydrocarbon ring or aromatic heterocycle formed by Q may have a substituent, and as the substituent, those mentioned in the above W can be applied.

  The aromatic hydrocarbon ring or aromatic heterocycle formed by Q may further form a condensed ring with another ring. Examples of the condensed ring include a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring. , Pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, oxadiazole ring, thiazole ring, thiadiazole ring, furan ring, thiophene ring, selenophene ring, silole ring, gelmol ring, phosphole ring and the like. The above substituent and condensed ring may further have a substituent and may be further condensed with another ring. As the substituent, those mentioned as W above can be applied.

  The aromatic hydrocarbon ring or aromatic heterocycle formed by Q is preferably a benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole. Ring, furan ring, thiophene ring, more preferably benzene ring, pyridine ring, pyrazine ring, pyrrole ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, thiophene ring, more preferably benzene ring, A pyridine ring, a pyrazine ring, a pyrazole ring, an imidazole ring and a thiophene ring, particularly preferably a benzene ring, a pyridine ring and a pyrazine ring, particularly preferably a benzene ring. Plural Qs may be the same or different, but are preferably the same, and most preferably the ring consisting of Q is all benzene rings.

The π-conjugated compound used in the present invention is more preferably used as an n-type material. In the present invention, the n-type material refers to a material having a higher electron transport capability than a hole transport capability. Therefore, when the π-conjugated compound A is phthalocyanine and its analog, the phthalocyanine represented by the general formula 2 and its analog have an electron withdrawing group bonded to the ring formed by Q, or Q It is particularly preferable that the ring formed by is an electron-deficient aromatic heterocycle. There is no restriction | limiting in particular as an electron withdrawing group, For example, refer to Chem. Rev. 1991, 91, 165. In which the Hammet value is a positive value, and specific examples thereof include a halogen atom, a cyano group, a nitro group, a perfluoroalkyl group, —CO—R ¹ , —CO—CO—. _{^{R 1, -SO-R 1,}} -SO 2 -R 1, -C (= NR 2) -R 1, -S (= NR 2) -R 1, -S (= NR 2) 2 -R ¹ , —P (═O) R ¹ ₂ , —O—R ³ , —S—R ³ , —N (—R ² ) —CO—R ¹ , —N (—R ² ) —SO—R ¹ , _{^{-N (-R 2) -SO 2 -R}} 1, -N (-R 2) -C (= NR 2) -R 1, -N (-R 2) -S (= NR 2) 2 - R ^1, and ^{-N (-R 2) -P (=} O) include groups represented by ^R _{1 2.} Where R ¹ is a hydrogen atom, alkyl group, aryl group, heterocyclic group, amino group, alkyloxy group, aryloxy group, heterocyclic oxy group, hydroxy group, alkylthio group, arylthio group, heterocyclic thio group, or mercapto Represents a group. Specific examples of W include those shown as examples of these substituents. R ² represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, or a phosphoryl group. Specific examples of W include those shown as examples of these substituents. R ³ represents a perfluoroalkyl group, a cyano group, an acyl group, a sulfonyl group, or a sulfinyl group. Specific examples of W include those shown as examples of these substituents.

The groups represented by R ¹ , R ² and R ³ may be further substituted with a substituent (for example, a substituent represented by W). Specific examples of such a substituent include a halogen atom (fluorine atom). , Chlorine atom, bromine atom or iodine atom), alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group (regarding the position of substitution) A quaternized heterocyclic group containing a nitrogen atom (eg, pyridinio group, imidazolio group, quinolinio group, isoquinolinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxyl group or salt thereof, sulfonyl Carbamoyl, acylcarbamoyl, sulfamoylcarbamoyl, carbazoyl, oxalyl, oxy Moyl group, cyano group, thiocarbamoyl group, hydroxyl group, alkoxy group (including groups containing repeating ethyleneoxy group or propyleneoxy group units), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) Carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonyl Amino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, acyls Rufamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocycle) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or its salt, sulfamoyl group, acylsulfur group A famoyl group, a sulfonylsulfamoyl group or a salt thereof, a group containing a phosphoric acid amide or a phosphoric ester structure, a silyloxy group (for example, trimethylsilyloxy, t-butyldimethylsilyloxy), and a silyl group (for example, trimethylsilyl, t -Butyldimethylsilyl, phenyldimethylsilyl) and the like.

  The electron withdrawing group is preferably a fluorine atom, a chlorine atom, a nitro group, a cyano group, a perfluoroalkyl group, a sulfonyl group, a sulfo group, an ester group, a carbonyl group, or an electron-deficient aromatic heterocyclic group (described later). More preferably a fluorine atom, a chlorine atom, a nitro group, a cyano group, a perfluoroalkyl group or a sulfonyl group, and still more preferably a fluorine atom or a chlorine atom.

  An electron-deficient aromatic heterocycle is a heterocycle having a lower electron density than a benzene ring, and may be said to have a molecular structure that is less susceptible to oxidation and more susceptible to reduction than a benzene ring. Preferably it is a C2-C10 thing containing 1 or more of nitrogen atoms, More preferably, it is a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, an oxazole ring, an oxadiazole ring, a thiazole ring, a thiadiazole ring. , A quinoline ring, a silole ring, or a gelmol ring, particularly preferably a pyridine ring or a pyrazine ring.

  The π-conjugated compound A and compound B used in the present invention are particularly preferably fluorinated phthalocyanines (compounds A2 and B2) of the following general 3 from the viewpoint of semiconductor characteristics and compound stability.

(In the formula, M represents a metal atom or a hydrogen atom (in the case of a hydrogen atom, bonded to a nitrogen atom of an isoindole ring and a nitrogen atom of an isoindoline ring), m represents a natural number, R represents a substituent, n represents a natural number. When there are a plurality of R, the plurality of R may be the same or different.

  In the formula, M and R are the same as those in the general formula 2, and the preferred ranges are also the same. m is preferably 1 to 16, and more preferably 4 to 15. The preferred range of n is the same as described above.

  As described above, the energy levels of Compound A and Compound B are preferably close. Therefore, when the π-conjugated compound A is a fluorinated phthalocyanine represented by the general formula 3, it is preferable that the solubilizing group R of the compound B is simultaneously an electron withdrawing group.

As the electron-withdrawing group, those described above can be used, but a group represented by -LR 'is preferably used. Here, L is _{^{** -SO 2 - *, ** -SO}} 3 - *, ** -SO 2 N (-) 2 *, ** -SO- *, ** -CO- *, ** - _{^{CON (-) 2 *, **}} -COO- *, ** -COCO 2 - *, and ^** -COCON _(-) represents a group selected from groups represented by the ₂ ^*. ** is bonded to the phthalocyanine skeleton at this position, and * is bonded to R ′ at this position. When a plurality of R ′ are bonded, each R ′ may be the same or different.

L is preferably _{^{** -SO 2 - *, ** -SO}} 2 N (-) 2 *, ** -CO- *, ** -CON (-) is represented by ₂ ^* or ^** -COO- ^* that group is used, more preferably _{^{** -SO 2 - *, ** -SO}} 2 N (-) 2 * or ^** -CON _{(-) 2} ^* group represented by is used, and particularly preferably ^** -SO ₂ - ^*, or ^** -SO ₂ N _(-) groups represented by ₂ ^* used.

  R 'represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Specific examples of the aforementioned W include alkyl groups, aryl groups, and heterocyclic groups. R ′ is preferably an alkyl group, an aryl group or a heterocyclic group. When R ′ is an alkyl group, an aryl group or a heterocyclic group, these may be further substituted with another substituent (for example, a substituent represented by W).

  R ′ is more preferably an alkyl group or an aryl group, and particularly preferably an alkyl group. R 'has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. R ′ preferably contains a branched alkyl group from the viewpoint of improving solubility in a solvent, but it is preferable to use a linear alkyl group from the viewpoint of improving semiconductor characteristics, depending on the application and required characteristics. Appropriate ones can be selected.

  The preferable specific example of the organic-semiconductor composition of this invention is shown below. However, the present invention is not limited to the following examples. In the following expression, “+” indicates a uniform mixture of both, and the description of the solvent existing in the above range as the composition is omitted.

  Each component (compounds A and B) of the organic semiconductor composition of the present invention is synthesized with reference to “Organic Field-Effect Transistors” (2007, CRC Press), pages 159 to 228, and papers cited therein. Can do.

  In the case where the organic semiconductor composition of the present invention is a phthalocyanine, the synthesis thereof is described in pages 1 to 62 of Shirai Yasuyoshi, Kobayashi Nagao, edited by “Phthalocyanine—Chemistry and Function” (IPC, 1997). It can be carried out according to the method described on pages 29-77 of Ryo Takahashi, Keiichi Sakamoto, and Eiko Okumura edited by “Phthalocyanine as a functional pigment” (IPC, 2004).

  Typical methods for synthesizing phthalocyanines include the Weiler method, phthalonitrile method, lithium method, subphthalocyanine method, and chlorinated phthalocyanine method described in these documents. In the present invention, the phthalonitrile method can be preferably used. When synthesizing phthalocyanines having a ratio of 1: 3, 2: 2, or 3: 1 of isoindoline rings having different structures, for example, by mixing two or more phthalonitrile derivatives in a desired ratio and reacting them, A phthalocyanine mixture containing a phthalocyanine derivative having the intended isoindoline ring ratio as the main product can be obtained. This method is a simple synthesis method with relatively short steps, although the selectivity of the reaction is inferior to that of the subphthalocyanine method. In order to selectively obtain a phthalocyanine derivative having a ratio of 1: 3 or 3: 1, for example, a sub-phthalocyanine derivative having three isoindoline rings centered on boron and a different 1,3-diiminoisotope are used. A subphthalocyanine method in which an indoline derivative or the like is reacted can be preferably used.

  Any reaction conditions may be used in the ring-forming reaction of phthalocyanines. In the ring formation reaction, it is preferable to add various metals to be the central metal of phthalocyanines, but a desired metal may be introduced after synthesizing a phthalocyanine having no central metal. The reaction solvent is not particularly limited, but is preferably a high boiling point solvent. In order to promote the ring formation reaction, it is preferable to use an acid or a base, and it is particularly preferable to use a base. Optimum reaction conditions vary depending on the structure of the target phthalocyanine derivative, but can be set with reference to specific reaction conditions described in the above-mentioned documents.

  As raw materials used for the synthesis of the above phthalocyanine derivatives, derivatives such as phthalic anhydride, phthalimide, phthalic acid and salts thereof, phthalic acid diamide, phthalonitrile, 1,3-diiminoisoindoline can be used. These raw materials can be synthesized by a conventional method by a known method.

  The organic semiconductor composition of the present invention may be obtained by mixing the respective components to obtain a composition, or may be synthesized as a composition at the time of synthesis, but preferably the one obtained as a mixture of organic semiconductors at the time of synthesis is used. Is the case. Among these, phthalonitrile (or phthalic anhydride, phthalimide, phthalic acid and salts thereof, phthalic acid diamide, 1,3-diiminoisoindoline, etc.) having two or more different substituents is particularly preferable. In this case, a mixture of phthalocyanines is obtained, and an organic semiconductor composition is produced using the mixture.

  Hereinafter, the application of the composition of the present invention as an organic semiconductor will be described in more detail.

The organic semiconductor in the present invention is an organic material exhibiting semiconductor characteristics. Similar to semiconductors made of inorganic materials, there are p-type organic semiconductors that conduct holes as carriers and n-type organic semiconductors that conduct electrons as carriers. The ease of carrier flow in the organic semiconductor is represented by carrier mobility μ. Although it varies depending on the application, in general, the mobility should be high, preferably 10 ⁻⁷ cm ² / Vs or more, and more preferably 10 ⁻⁵ cm ² / Vs or more. The mobility can be obtained by characteristics when a field effect transistor (FET) element is manufactured or by a time-of-flight measurement (TOF) method.

  Any method may be used to form a thin film containing an organic semiconductor compound using the organic semiconductor composition of the present invention, but the film is formed by a vacuum process or a solution process. Specific examples of vacuum process film formation include physical vapor deposition such as vacuum deposition, sputtering, ion plating, molecular beam epitaxy (MBE), or chemical vapor deposition (CVD) such as plasma polymerization. Law. Solution process film formation is a method in which an organic compound is dissolved in a solvent capable of dissolving it, and the solution is used to form a film. Specifically, a cast method, a blade coating method, a wire bar coating method, a spray coating method is used. Method, dipping (dipping) coating method, bead coating method, air knife coating method, curtain coating method, ink jet method, spin coating method, Langmuir-Blodgett (LB) method, etc., casting method, spin coating method and ink jet method Is preferably used.

  In the present invention, it is preferable to form a film by a solution process. The organic semiconductor of the present invention can be formed to a thickness of several mm to several nm or less by solution process film formation. The film thickness is not particularly limited depending on the type of electronic device, but is preferably 1 nm to 50 μm, more preferably 10 nm to 1 μm.

  When an organic semiconductor layer is formed using a solution process, a material for forming the layer, or the material and a binder resin are mixed with a suitable organic solvent (for example, hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, Hydrocarbon solvents such as 1,2-dichlorobenzene, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, di Halogenated hydrocarbon solvents such as chlorobenzene and chlorotoluene, for example, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate, such as methanol, propanol, butanol, and pentano Alcohol solvents such as hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, for example, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, such as N, N-dimethylformamide, N, N-dimethyl A polar solvent such as acetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethyl sulfoxide) and / or water to form a coating solution, and thin films by various coating methods Can be formed. In the coating solution, the concentration of the organic semiconductor compounds A and B in the composition of the present invention is preferably 0.1 to 80% by mass, more preferably 0.1 to 10% by mass, A film having an arbitrary thickness can be formed.

  In the composition of the present invention, it is also possible to use a resin binder. In this case, as the resin binder, polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, Insulating polymers such as polymethyl acrylate, cellulose, polyethylene, and polypropylene, and copolymers thereof, photoconductive polymers such as polyvinyl carbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene. be able to. The resin binder may be used alone or in combination. In consideration of the mechanical strength of the film, a resin binder having a high glass transition temperature is preferable, and in consideration of charge mobility, a resin binder, a photoconductive polymer, or a conductive polymer having a structure containing no polar group is preferable. It is preferable not to use a resin binder in view of the characteristics of the organic semiconductor, but it may be used depending on the purpose. The amount of the resin binder to be used is not particularly limited, but is preferably 0.1 to 90% by mass, more preferably 0.1 to 50% by mass, and further preferably 0.1 to 30% in the organic semiconductor film. Used in mass%.

  The substrate surface may be treated to control unevenness, smoothness, hydrophilicity / hydrophobicity, intermolecular interaction, etc., and to control the film morphology and molecular orientation, for example, the silicon dioxide surface And a method of surface-treating by coating with hexamethyldisilazane (HMDS) or octadecyltrichlorosilane (OTS).

  During film formation, the substrate may be heated or cooled, and the morphology and molecular orientation state of the film can be controlled by changing the temperature of the substrate. Although there is no restriction | limiting in particular as temperature of a board | substrate, It is preferable that it is between 0 degreeC and 200 degreeC.

  The organic semiconductor composition of the present invention is particularly suitable for film formation by a solution process. In general, in order to form a film by a solution process, it is necessary that the material is dissolved in the above-described solvent or the like, but it is sometimes insufficient to simply dissolve the material. Usually, even a material for forming a film by a vacuum process can be dissolved in a solvent to some extent. However, in the film formation method by the solution process, there is a process in which the solvent evaporates and a thin film is formed after the material is dissolved and applied, and a material that is not suitable for the solution process film formation has high crystallinity. Therefore, it is difficult to form a good thin film due to crystallization in this process. On the other hand, the organic semiconductor composition of the present invention is also excellent in that crystallization hardly occurs.

  Any electronic device may be used in the present invention, but a device using an electronic element having a film structure is preferable. Examples of the electronic device using the electronic element of the present invention include an organic photoelectric conversion element, an organic transistor, an organic electroluminescent element, a gas sensor, an organic rectifying element, an organic inverter, and an information recording element. The organic photoelectric conversion element can be used for both optical sensor applications (solid-state imaging elements) and energy conversion applications (organic solar cells). Preferably, they are an organic photoelectric conversion element, an organic transistor, and an organic electroluminescent element, More preferably, they are an organic photoelectric conversion element and an organic transistor. Hereinafter, typical examples of these preferred embodiments will be described in detail with reference to the drawings, but the present invention is not limited to these embodiments.

  FIG. 1 is a cross-sectional view schematically showing the structure of an organic field effect transistor (FET) element using the electronic element of the present invention. The transistor in FIG. 1 has a laminated structure as a basic structure, and a substrate 11 (for example, a polyester film such as polyethylene naphthoate (PEN) or polyethylene terephthalate (PET), polyimide film, ceramic, silicon, quartz, Glass, etc.) is disposed, an electrode 12 is provided on a part of the upper surface thereof, and an insulator layer 13 is provided so as to cover the electrode and to be in contact with the substrate at a part other than the electrode. Furthermore, the organic semiconductor layer 14 is provided on the upper surface of the insulator layer 13, and the two electrodes 15a and 15b are disposed separately on a part of the upper surface. The constituent material of the electrode 12, the electrode 15a, and the electrode 15b can be used without particular limitation as long as it exhibits conductivity. Cr, Al, Ta, Mo, Nb, Cu, Ag, Au, Pt, Pd, Any known conductive material such as a metal material such as In, Ni, or Nd, an alloy material thereof, a carbon material, or a conductive polymer can be used without any particular limitation. 1 is called a top contact type element, a bottom contact type element in which the electrodes 15a and 15b are under the organic semiconductor layer can also be preferably used.

  The gate width (channel width) W and the gate length (channel length) L are not particularly limited, but the ratio W / L is preferably 10 or more, and more preferably 20 or more.

  The thickness of each layer is not particularly limited, but when it is necessary to make the transistor thinner, for example, the thickness of the entire transistor is preferably 0.1 to 0.5 μm. The thickness is preferably 10 to 400 nm, and the thickness of the electrode is preferably 10 to 50 nm.

  The material constituting the insulating layer is not particularly limited as long as the necessary insulating effect can be obtained. For example, silicon dioxide, silicon nitride, polyester insulating material, polycarbonate insulating material, acrylic polymer insulating material, epoxy resin insulating material, polyimide Insulating materials, polyparaxylylene resin-based insulating materials, and the like can be given.

  In order to shield the device from the atmosphere and moisture and improve the storage stability of the device, the entire device is sealed with a metal sealing can, an inorganic material such as glass, silicon nitride, and alumina, or a polymer material such as parylene. Also good.

  FIG. 2 is a sectional view schematically showing the structure of an organic thin film photoelectric conversion element using the electronic element of the present invention. The element of FIG. 2 has a laminated structure, and a substrate 21 (for example, a polyester film such as polyethylene naphthoate (PEN) or polyethylene terephthalate (PET), polyimide film, ceramic, silicon, quartz, glass, etc.) in the lowermost layer. The electrode layer 22 is provided on the upper surface, the layer 23 including the p-type organic semiconductor and / or the n-type organic semiconductor is provided thereon, and the electrode layer 24 is provided on the upper surface. Between the electrode layers 22 and 24 and the layer 23 containing a p-type organic semiconductor and / or an n-type organic semiconductor, a buffer layer that enhances surface smoothness, a carrier injection layer that promotes injection of holes or electrons from the electrode. In addition, a carrier block layer that blocks holes or electrons may be included.

The material used for the electrode layer 22 is not particularly limited as long as it transmits visible light or infrared light and exhibits conductivity. The transmittance of visible light or infrared light is preferably 60% or more, more preferably 80% or more, and most preferably 90% or more. Such materials include ITO, IZO, SnO ₂ , ATO (antimony-doped tin oxide), ZnO, AZO (Al-doped zinc oxide), GZO (gallium-doped zinc oxide), TiO ₂ , FTO (fluorine-doped tin oxide). A transparent conductive oxide such as ITO is preferred, and ITO or IZO is particularly preferred from the viewpoint of process suitability and smoothness.

  The material used for the electrode layer 24 is not particularly limited as long as it exhibits conductivity, as in the transistor described above, but a material having high light reflectivity is preferable and particularly preferable from the viewpoint of improving light utilization efficiency. These are Al, Pt, W, Au, Ag, Ta, Cu, Cr, Mo, Ti, Ni, Pd, and Zn.

  There is no particular limitation on the thickness of each layer, and the preferable thickness of the entire element, the thickness of each layer, the thickness of the electrode layer, and the like are the same as those of the above-described transistor.

  In order to improve the storage stability of the element, the entire element may be sealed in the same manner as the transistor described above.

  When using a photoelectric conversion element as a solar cell for energy conversion, in order to efficiently absorb sunlight and increase energy conversion efficiency, light is emitted to a long wavelength region of 600 nm or more, particularly preferably to a near infrared region of 700 nm or more. It is preferable to use a material that absorbs light and performs photoelectric conversion.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

[Synthesis Example 1] (Preparation of organic semiconductor compositions 1 and 1 ')
Under a nitrogen atmosphere, tetrafluorophthalonitrile 3.0 g (15 mmol), 4-octylsulfonylphthalonitrile 1.5 g (5.0 mmol), and copper (I) chloride 0.99 g (10 mmol) were mixed with 1-methyl-2-pyrrolidone. It was dissolved in 50 mL and stirred at 180 ° C. for 3 hours. After allowing to cool to room temperature, the reaction mixture was poured into 200 mL of 5% hydrochloric acid to precipitate blue crystals. The crystals were collected by suction filtration, washed with 5% hydrochloric acid, washed with water, washed with acetonitrile, and dried. The mixture was further boiled with 50 mL of acetonitrile for 1 hour and allowed to cool to room temperature, and then the precipitate was collected by suction filtration and dried. The mixture was further boiled with 50 mL of hexane for 1 hour and allowed to cool to room temperature. The precipitate was collected by suction filtration and dried to obtain 2.2 g (yield 45%) of organic semiconductor 1 (Chemical formula 6) (melting point) > 200 ° C.). Organic semiconductor 1 (5 mg) was dissolved in a mixed solvent of 1,2-dichlorobenzene (HPLC grade, 1 mL) / N, N-dimethylacetamide (HPLC grade, 1 mL), and toluene (HPLC grade, 5 μL) was added. The organic semiconductor composition 1 of the present invention was obtained as a solution. Further, organic semiconductor 1 (10 mg) is dissolved in a mixed solvent of 1,2-dichlorobenzene (HPLC grade, 1 mL) / N, N-dimethylacetamide (HPLC grade, 1 mL), and toluene (HPLC grade, 10 μL) is added. Thus, the organic semiconductor composition 1 ′ of the present invention was obtained as a solution.

The sum Σσ of the Hammet constants of the components in the organic semiconductor 1 is σ = (σ _m + σ _p ) / 2 = (0.34 + 0.06) /2=0.20 for F ₁₆ CuPc. 16 and Σσ = 3.20. For FPc-1, using the value of the SO ₂ Et group having the closest structure as the σ value of the SO ₂ C ₈ H ₁₇ group, σ = (σ _m + σ _p ) / 2 = (0.66 + 0.77) / 2 = 0.72, so Σσ = 3.12 with 12 F atoms and ₁₇ SO ₂ C ₈ H groups. Similarly, FPc-2 is Σσ = 3.03. FPc-3 is Σσ = 2.95. Therefore, the differences of the total sum Σσ of Hammet constants of FPc-1, FPc-2, and FPc-3 having solubilizing groups from F ₁₆ CuPc are as small as 0.08, 0.17, and 0.25, respectively.

The composition ratio of the organic semiconductor 1 as determined by liquid chromatography mass spectrometry (LCMS) _{is, (F 16 CuPc) :( FPc} -1) :( FPc-2) :( FPc-3) = 15.5: 54.0 : 26.4: 4.1 (the molar absorption intensity of (F ₁₆ CuPc), (FPc-1), (FPc-2), (FPc-3) at a detection wavelength of 254 nm is almost the same, The ratio obtained from the area is equal to the molar ratio). (Measurement conditions: TSK gel ODS-80Ts (2 mmφ × 150 mm), eluent: A / B (volume ratio 3: 7) from 0 to 15 minutes, A / B from 15 to 20 minutes (same as 15: 85) (eluent A: water, eluent B: tetrahydrofuran / methanol (9: 1) mixed solution), flow rate 0.2 mL / min, detection wavelength 254 nm, atmospheric pressure chemical ionization (APCI) -mass spectrometry (MS ) To determine the structure (by MS, retention time = 8.185 min peak is F ₁₆ CuPc, retention time = 11.676 min peak is (FPc-1), retention time = 13.905 min peak is ( FPc-2), retention time = 14.350 minutes peak was confirmed to be (FPc-3)), and from 0 minutes to 4 minutes, the peak was detected by blank measurement, so the measurement was taken from 4 minutes).

  Next, in the drawing, a liquid chromatography diagram (FIG. 3) and a mass spectrum diagram (FIG. 4) of the organic semiconductor 1 of the present invention (matrix-assisted laser desorption ionization (MALDI) -time-of-flight (TOF) -mass spectrometry (Measured with a meter (MS)), IR spectrum diagram (FIG. 5), absorption spectrum diagram of 1-methyl-2-pyrrolidone solution (FIG. 6), CV (cyclic voltammetry) measurement result of N, N-dimethylacetamide solution (FIG. 7) is shown.

[Synthesis Example 2] (Preparation of Organic Semiconductor Composition 2)
In a nitrogen atmosphere, 1.0 g (5.0 mmol) of tetrafluorophthalonitrile, 0.5 g (1.7 mmol) of 4-octylsulfonylphthalonitrile, and 0.38 g (1.7 mmol) of zinc bromide were added to 5 mL of 1-chloronaphthalene. And stirred at 180 ° C. for 2 hours. After allowing to cool to room temperature, the reaction mixture was poured into 200 mL of hexane, and the precipitate was collected by suction filtration and washed well with hexane. By purifying this solid by column chromatography using silica gel (developing solvent: toluene / THF = 9/1 to 3/1), 75 mg of organic semiconductor 2 (mixture of the compounds shown in Chemical formula 7) (yield 5) %) (Melting point> 200 ° C.). Organic semiconductor 2 (5 mg) was dissolved in 1,2-dichlorobenzene (HPLC grade, 1 mL) / N, N-dimethylacetamide (HPLC grade, 1 mL) mixed solvent, and toluene (HPLC grade, 5 μL) was added. An organic semiconductor composition 2 of the present invention was obtained.

According to the same calculation as that of the organic semiconductor 1, the sum of Hammet values of each component of the organic semiconductor 2 of the present invention is Σσ = 3.20 for F ₁₆ ZnPc, Σσ = 3.12 for FPc-4, and Σσ for FPc-5. = 3.03, FPc-6 is Σσ = 2.95. Therefore, the differences of the sum Σσ of Hammet constants of FPc-4, FPc-5, and FPc-6 having solubilizing groups from F ₁₆ ZnPc are as small as 0.08, 0.17, and 0.25, respectively.

The composition ratio of the organic semiconductor 2 determined by liquid chromatography mass spectrometry (LCMS) is (F ₁₆ ZnPc) :( FPc-4) :( FPc-5) :( FPc-6) = 13: 54: 16: 17 It is.

[Example 1]
(Experimental conditions)
The organic semiconductor composition 1 of the present invention is cast on a quartz substrate heated to 100 ° C. with a hot plate, and a solid film having a thickness of 1 μm or less and a uniform thickness is formed, whereby a sample for absorption spectrum measurement (solid film) is obtained. Obtained. Similarly, an FET characteristic measurement sample was obtained by casting on an FET characteristic measurement substrate heated to 100 ° C. and forming a solid film having a uniform thickness of 1 μm or less. As the substrate for measuring FET characteristics, the substrate shown in FIG. 8 was used. A substrate of a bottom contact structure provided with gold / chrome (gate width W = 100000 μm, gate length L = 100 μm) arranged in a comb shape as an electrode and SiO ₂ (film thickness 200 nm) as an insulating film was used. The absorption spectrum was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, MPC-2200 / UV-2400). The FET characteristics were measured under normal pressure and nitrogen atmosphere (in a glove box) using a semiconductor parameter analyzer (Agilent, 4156C) connected to a semi-auto prober (Vector Semicon, AX-2000).

(FET characteristics)
As shown in FIG. 9, the organic semiconductor 1 of the present invention exhibited good n-type FET characteristics. Expression I _d representing drain current I _d = (w / 2L) μC _i (V _g −V _th ) ² (where L is the gate length, W is the gate width, and C _i is the capacitance per unit area of the insulating layer) , V _g represents the gate voltage, and V _th represents the threshold voltage), the carrier mobility μ was determined, and the mobility of the organic semiconductor composition 1 was μ = 4.5 × 10 ⁻⁴ cm ² / Vs. Further, even when this element was taken out into the atmosphere and measured, only the mobility was reduced to about half, and there was almost no deterioration in characteristics. When the FET element was observed with an optical microscope and an electron microscope, the element of the present invention formed an organic film having a uniform film quality as shown in FIGS. Vertical stripes in the photograph of FIG. 10 indicate a source electrode and a drain electrode (the same applies to FIG. 13).

(Solid film absorption spectrum)
FIG. 12 (a) shows the absorption spectrum measurement result of the solid film of the organic semiconductor 1 of the present invention. This absorption spectrum is very similar to the solid film of F ₁₆ CuPc obtained by the vacuum deposition method (FIG. 12 (b)). In addition to the absorption around 680 nm derived from the monomer absorption of the phthalocyanine structure, Long wavelength absorption extending to the infrared region (700-800 nm) was observed. This result suggests the high molecular association property of the organic semiconductor composition 1 of the present invention, and this association property is considered to contribute to the expression of high electronic functions such as good FET characteristics.

[Example 2]
An FET element was produced by the same method as in Example 1 except that the organic semiconductor composition 2 was used instead of the organic semiconductor composition 1, and the FET characteristics were examined under the same conditions. Similar to Example 1, good n-type FET characteristics were exhibited. The mobility was μ = 6.3 × 10 ⁻⁵ cm ² / Vs.

[Comparative Example 1]
F ₁₆ CuPc (purchased from Aldrich and purified by sublimation) instead of organic semiconductor composition 1 was mixed with 1,2-dichlorobenzene (HPLC grade, 1 mL) / N, N-dimethylacetamide (HPLC grade, 1 mL) An FET element was produced by the same method as in Example 1 except that the obtained one was used, and the FET characteristics were examined under the same measurement conditions. As a result, the FET characteristics were not exhibited at all in a nitrogen atmosphere or in the air. When the element used for the measurement was observed with an optical microscope, it was found that the coating of F ₁₆ CuPc did not form a thin film due to low solubility and crystallization as shown in FIG.

[Comparative Example 2]
An FET device was fabricated in the same manner as in Comparative Example 1 except that F ₁₆ ZnPc (purchased from Aldrich and purified by sublimation) was used instead of F ₁₆ CuPc, and the FET characteristics were examined under the same measurement conditions. The FET characteristics were not shown at all even in a nitrogen atmosphere or in the air. When the element used for the measurement was observed with an optical microscope, it was found that the coating of F ₁₆ ZnPc did not form a thin film due to low solubility and crystallization.

Table 1 summarizes the above results and the characteristics of the comparative compounds (F ₁₆ CuPc, F ₁₆ ZnPc) formed by the vacuum deposition method described in the literature (Japanese Patent Laid-Open No. 11-251601). As shown in Table 1, an organic semiconductor material that has been conventionally poor in solubility in a solvent and has good characteristics but could not be used in solution process film formation is the organic semiconductor composition of the present invention. It has been found that solution process film formation is possible while maintaining the good semiconductor characteristics.

[Example 3]
(Photoelectric conversion characteristics)
The glass substrate on which the ITO electrode was patterned was subjected to ultrasonic cleaning in isopropyl alcohol and then dried. Further, UV ozone treatment was performed to remove organic contaminants on the ITO electrode surface. Next, PEDOT (poly (3,4-ethylenedioxythiophene)) / PSS (polystyrene sulfonic acid) aqueous solution (BaytronP (standard product)) is spin-coated (4000 rpm, 30 seconds) on the ITO substrate to form a film. A buffer layer having a thickness of about 50 nm was formed.

After drying at 120 ° C. for 1 hour, 10 mg of P3HT (poly (3-hexylthiophene), regioregular, Mw-87000, manufactured by Aldrich) and the organic semiconductor composition 1 ′ (about 2 mL) of the present invention were mixed and mixed. The solution was spin-coated (1000 rpm, 60 seconds) to form a photoelectric conversion layer having a thickness of 20 to 30 nm. On this photoelectric conversion layer, a metal electrode was formed by sequentially vacuum-depositing LiF to a thickness of 1 nm and aluminum to a thickness of 80 nm. It moved to the glove box, maintaining the vacuum, and sealed with a metal sealing can and a UV curable resin in a nitrogen atmosphere to obtain a photoelectric conversion element having an effective area of 0.04 cm ² . Photoelectric conversion characteristics were measured by irradiating white light (0.05 mW / cm ² ) using a xenon lamp (manufactured by Hamamatsu Photonics Co., Ltd., L2195) as a light source within an irradiation range of 1.5 mm in diameter from the ITO electrode side of the photoelectric conversion film While using a spectral sensitivity measuring device (Sumitomo Heavy Industries Advanced Machinery Co., Ltd.) equipped with a source meter (Keithley Co., 6430). The external quantum efficiency was determined from the value obtained by subtracting the dark current value from the photocurrent value. As shown in FIG. 14, it was found that the photoelectric conversion element composed of the organic semiconductor composition 1 ′ and P3HT exhibits photoelectric conversion characteristics in a wide wavelength range from the visible range to the near infrared range.

[Comparative Example 3]
In the same manner as in Example 3, except that a solution obtained by mixing ₁₀ mg of F ₁₆ CuPc with a mixed solvent of 1,2-dichlorobenzene (1 mL) / N, N-dimethylacetamide (1 mL) was used instead of the organic semiconductor composition 1 ′. A conversion element was produced and an attempt was made to measure photoelectric conversion characteristics by the same method. However, since the solubility of F ₁₆ CuPc in the solvent was low, a uniform film of the photoelectric conversion layer could not be obtained, resulting in a film with large irregularities. As a result, the element was short-circuited, and the characteristics could not be measured.

  As described above, an organic semiconductor material that exhibits good characteristics but is not suitable for solution process film formation due to low solubility can be used as the organic semiconductor composition of the present invention, thereby providing good characteristics as an organic semiconductor. It has been shown that solution process suitability can be imparted while retaining.

It is sectional drawing which shows roughly the structure of the organic field effect transistor element of this invention. It is sectional drawing which shows roughly the structure of the organic photoelectric conversion element of this invention. It is a figure which shows the liquid chromatography (HPLC) measurement result of the organic semiconductor 1. FIG. It is a figure which shows the mass spectrum (MALDI-TOF-MS) of the organic semiconductor 1. FIG. 1 is a diagram showing an IR spectrum of an organic semiconductor 1. FIG. It is a figure which shows the absorption spectrum of the 1-methyl-2-pyrrolidone solution of the organic semiconductor 1 ((lambda) _max = 674nm, (epsilon) = 7.6 * 10 < ⁴ >). N organic semiconductor 1, N-dimethylacetamide solution (c = 5.0mmol / L, supporting _electrolyte: Bu 4 NClO ₄₎ is a diagram showing a CV (cyclic voltammetry) measurements of. (E ^Red _1/2 = −0.42 V vs Ag / AgCl) It is a figure which shows the board | substrate for a field effect transistor characteristic measurement. It is a figure which shows the FET characteristic ((a) drain voltage-drain current characteristic, (b) drain voltage-drain current characteristic at the time of 100V application) of the organic-semiconductor composition 1 of this invention). It is an optical microscope photograph (500-times multiplication factor) of the FET element of the organic-semiconductor composition 1 of this invention. It is an electron micrograph (4000 times magnification) of the FET element of the organic semiconductor composition 1 of the present invention. (A) shows the absorption spectrum of the organic semiconductor composition 1 solid membrane of the present invention, and (b) a solid film of F ₁₆ CuPc obtained by the vapor deposition method by a coating. Is an optical microscope photograph of _F 16 CuPc coating was a comparative compound (500X magnification). It is a figure which shows the photoelectric conversion spectrum of the photoelectric conversion element using the organic-semiconductor composition 1 'of this invention.

Explanation of symbols

11 Substrate 12 Electrode 13 Insulator layer 14 Organic layer (semiconductor organic layer)
15a, 15b Electrode 21 Substrate 22 Electrode 23 Photoelectric conversion layer 24 Electrode 31 Substrate 32 Electrode 33 Insulator layers 34a, 34b Electrode 35 Organic substance layer (semiconductor organic substance layer)

Claims (12)

As an organic semiconductor component, π-conjugated compound A and at least one kind of compound B in which a part of hydrogen atoms or substituents of π-conjugated compound A are replaced with solubilizing groups R or hydrogen atoms (at least one is R) And the difference between the sum of the Hammet constants of the solubilizing group R of the compound B and the sum of the Hammet constants of the substituents to be replaced in the compound A is 1.0 or less, and at least one boiling point 40 The organic-semiconductor composition characterized by containing the solvent of 0.1-20 degreeC by mass ratio with respect to an organic-semiconductor component in 1/20 times or more and less than 1000 times.
(In the formula, R represents a substituent, and n represents a natural number. When there are a plurality of Rs, the plurality of Rs may be the same or different from each other. + Represents a homogeneous mixture of the two (the same applies hereinafter). ).)   The organic semiconductor composition according to claim 1, wherein the content of compound A and at least one kind of compound B in the organic semiconductor component is 10% by mass or more. The organic-semiconductor composition of Claim 1 or 2 represented by the following general formula 2 which the said composition contains the following (pi) conjugated compound A1 and compound B1, and consists of phthalocyanine or its analog.
(In the formula, M represents a metal atom or a hydrogen atom (when M is a hydrogen atom, two hydrogen atoms are bonded to nitrogen atoms of N ¹ and N ² , respectively.) Q represents an aromatic hydrocarbon ring or aromatic group. Represents a group of atoms necessary to form a group heterocycle, a plurality of Qs may be the same or different, R represents a substituent, n represents a natural number, and when R is a plurality, a plurality of R May be the same or different.)   The organic semiconductor composition according to claim 1, wherein at least one of the organic semiconductor components is an n-type organic semiconductor. The organic semiconductor composition according to claim 1, wherein the composition contains the following π-conjugated compound A2 and compound B2, and is represented by the following (General Formula 3).
(In the formula, M represents a metal atom or a hydrogen atom (in the case of a hydrogen atom, bonded to a nitrogen atom of an isoindole ring and a nitrogen atom of an isoindoline ring), m represents a natural number, R represents a substituent, n represents a natural number. When there are a plurality of R, the plurality of R may be the same or different. The organic semiconductor composition according to claim 1, wherein the solubilizing group R is —SO ₂ R ′ or —SO ₂ NR ′ ₂ (R ′ represents a substituent).   The manufacturing method of the organic-semiconductor composition in any one of Claims 1-6 using using an organic-semiconductor component by mixing and making it react with 2 or more types of phthalonitrile or its derivative (s).   The film | membrane formed using the organic-semiconductor composition in any one of Claims 1-6.   The film according to claim 8, wherein the film forming method is a solution process.   The organic electronic device using the organic-semiconductor composition in any one of Claims 1-6.   The organic transistor using the organic-semiconductor composition in any one of Claims 1-6.   The organic photoelectric conversion element using the organic-semiconductor composition in any one of Claims 1-6.