TW201307427A - Method for producing organic photoelectric conversion element - Google Patents

Abstract

Provided is a method for producing an organic photoelectric conversion element which comprises a pair of electrodes and an activating layer with polymer compounds set between the pair of electrodes. An organic photoelectric conversion element with an excellent photoelectric comversion efficiency can be produced by the method for producing organic photoelectric conversion element compnsing an activating layer formed from a liquid containing polymer compounds and fluorine-containing solvent.

Description

Method for manufacturing organic photoelectric conversion element

The present invention relates to a method of producing an organic photoelectric conversion element.

The organic photoelectric conversion element has an advantage of reducing the number of layers of the organic layer in the element, and is capable of producing an organic layer by a printing method, and can be easily and inexpensively produced when compared with an inorganic photoelectric conversion element. However, the photoelectric conversion efficiency of the organic photoelectric conversion element is not good, which hinders its practical use.

JP-A-2009-158734 discloses that an organic photoelectric conversion element is produced by forming an active layer using a solution of P3HT and o-dichlorobenzene as a polymer compound.

However, the organic photoelectric conversion element obtained by this method has insufficient photoelectric conversion efficiency.

The present invention provides an organic photoelectric conversion element having high photoelectric conversion efficiency.

In other words, the present invention provides a method for producing an organic photoelectric conversion device, which is a method for producing an organic photoelectric conversion device including a pair of electrodes and an active layer containing a polymer compound between a pair of electrodes, and the active layer may include a polymer. The compound is formed with a liquid of a fluorine-containing solvent.

The reduction ratio of each member in the drawings shown in the following description may be different from the actual one. Meanwhile, in the organic photoelectric conversion element, although a member such as a wire of an electrode is also present, since it is not directly related to the description of the present invention, It is omitted from the description and the drawing. Meanwhile, in the following description, one of the substrate thickness directions may be referred to as "upper" or "upper", and the other of the substrate thickness directions may be "lower" or "lower". This upper and lower relationship is set for the convenience of explanation, and is not necessarily applicable to the steps in the actual manufacture of the organic photoelectric conversion element and the conditions of use.

The basic configuration of the organic photoelectric conversion device of the present invention has a configuration in which a pair of electrodes and an active layer are provided. At least one of the pair of electrodes is typically transparent or translucent. In an organic photoelectric conversion element, the anode is usually a transparent or translucent electrode. The organic photoelectric conversion element may also have an opaque electrode. When the organic photoelectric conversion element has an opaque electrode, the opaque electrode is usually a cathode. The active layer in the organic photoelectric conversion element is positioned between a pair of electrodes. The active layer may be one layer or a plurality of layers. Meanwhile, a layer other than the active layer may be provided between the pair of electrodes, and this layer is referred to as an intermediate layer in this specification.

The active layer contains one or more organic compounds. At least one of the organic compounds is a polymer compound. Examples of the organic compound include an electron-donating compound (p-type semiconductor) and an electron-accepting compound (n-type semiconductor). The active layer may be a single layer or a laminate in which a plurality of layers are overlapped. The form of the active layer may be, for example, a layer formed of an electron-donating compound (electron-donating layer) and a layer formed of an electron-accepting compound (electron-accepting layer) are superimposed into a so-called pn heterojunction type. A bulk heterojunction type in which a bulk heterojunction structure is formed by mixing an electron-donating compound and an electron-accepting compound. The active layer in the present invention may be in any one of them.

In the organic photoelectric conversion device of the present invention, the active layer is formed of a solution containing a polymer compound and a fluorine-containing solvent. The active layer is preferably formed by coating a solution containing a polymer compound and a fluorine-containing solvent on one of the electrodes.

An example of the layer configuration of the organic photoelectric conversion element will be described with reference to Figs. 1 to 3 . Fig. 1 to Fig. 3 are diagrams each showing an example of a layer configuration of an organic photoelectric conversion element. After the first drawing, the second drawing will be described only in the difference from the first drawing, and the third drawing will be described only in the difference from the first drawing and the second drawing.

In the example of the first embodiment, the laminated body in which the active layer 40 is sandwiched between the first electrode 32 and the second electrode 34 is mounted on the substrate 20 to constitute the organic photoelectric conversion element 10. When the light is collected from the substrate 20 side, the substrate 20 is transparent or translucent.

At least one of the first electrode 32 and the second electrode 34 is transparent or translucent. When light is collected from the substrate 20 side, the first electrode 32 is transparent or translucent.

Which of the first electrode 32 and the second electrode 34 is an anode or a cathode is not particularly limited. For example, when the organic photoelectric conversion element 10 is formed by sequentially laminating from the side of the substrate 20, when a vapor deposition method is used for film formation of a cathode (for example, aluminum or the like), vapor deposition is preferably carried out in a subsequent step. Therefore, in this case, it is preferable that the first electrode 32 is an anode and the second electrode 34 is a cathode. Meanwhile, in this case, the aluminum electrode may not be transparent or translucent due to the thickness setting. Therefore, in order to illuminate the substrate 20 side, it is preferable to form the substrate 20 and the first electrode 32 to be transparent or translucent.

In the example of FIG. 2, the active layer 40 is composed of the first active layer 42 and the first 2 The active layer 44 is composed of two layers and is a pn heterojunction type active layer. One of the first active layer 42 and the second active layer 44 is an electron receiving layer, and the other layer is an electron supply layer.

In the example of Fig. 3, the first intermediate layer 52 and the second intermediate layer 54 are provided. The respective positions are such that the first intermediate layer 52 is positioned between the active layer 40 and the first electrode 32, and the second intermediate layer 54 is positioned between the active layer 40 and the second electrode 34. It is also possible to provide only one of the first intermediate layer 52 and the second intermediate layer 54. Meanwhile, in Fig. 3, although each intermediate layer is described in a single layer, each intermediate layer may be composed of a plurality of layers.

The intermediate layer can have various functions. When the first electrode 32 is set as the anode, the first intermediate layer 52 may be, for example, a hole transport layer, an electron blocking layer, a hole injection layer, and a layer having other functions. At this time, the second electrode 34 is a cathode, and the second intermediate layer 54 may be, for example, an electron transport layer, an electron blocking layer, and a layer having other functions. On the other hand, when the first electrode 32 is used as the cathode and the second electrode 34 is used as the anode, the position of the intermediate layer can be changed as needed.

The polymer compound of the electron-donating compound or the electron-accepting compound contained in the active layer is not particularly limited, and thus the relative order of the level of the compound can be determined. The polymer compound includes a ring structure represented by the following. And a polymer compound having a structure such as methylcyclobutane, 4-ethylcyclohexane, xylene, styrene, ethylbenzene, thiophene, imidazole, thiazole, pyrrole or oxazole. At the same time, it may also include ethylene imine, ethylene oxide, ethylene sulfide, acetylene oxide, acetylene sulfide, azetidine, 1,3-epoxy. Propane, trimethylene sulfide, oxetium ion (oxetium ion), thietene ion (thietium ion), pyrrolidine, tetrahydrofuran, tetrahydrothiophene, pyrrole, furan, thiophene, piperazine Pyridine, tetrahydropyran, tetrahydrothiopyran, thiapyran, hexamethyleneimine, hexylene oxide, cyclohexane, azatropylidene, oxygen A polymer compound having a structure such as oxycycloheptatriene or Thiepin. Further, examples thereof include ruthenium, phenanthrene, fused tetraphenyl, 1,2-benzopyrene, hydrazine, triphenylene, tetraphene, pentacene, and hydrazine ( Picene), anthracene, anthracene, anthracene, naphthalene, benzopyrene, dibenzophenanthracene, benzothiophene, quinoxaline, anthracene, isoindole, benzimidazole, anthracene, quinoline, isoquine Porphyrin, cinnoline, pteridine, chromene, isobenzopyran, acridine, xanthene, carbazole, porphyrin, Chlorin, cholesteric A polymer compound of the same structure.

Examples of the polymer compound contained in the active layer include a polymer compound having a structural unit represented by the formula (1).

[In the formula, Ar ¹ and Ar ^{2 are the} same or different and each represents a trivalent aromatic group. Z represents -O-, -S-, -C(=O)-, -CR ¹ R ² -, -S(=O)-, -SO ₂ -, -Si(R ³ )(R ⁴ )-, -N(R ⁵ )-, -B(R ⁶ )-, -P(R ⁷ )- or -P(=O)(R ⁸ )-. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are the} same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or an aromatic group. Oxyl, arylthio, aralkyl, aralkoxy, aralkylthio, decyl, decyloxy, decylamino, quinone imine, imine, amine, substituted amine, substituted hydrazine A substituted methoxy group, a substituted oxime thio group, a substituted guanylamino group, a monovalent heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an aralkenyl group, an aryl alkynyl group, a carboxyl group or a cyano group. n represents 1 or 2. If n is 2, 2 Zs may be the same or different. ]

The polymer compound having a structural unit represented by the formula (1) may be a polymer compound containing any structural unit of the following formulas (2-1) to (2-10).

[wherein, R ²¹ to R ⁴² each independently represent a hydrogen atom or a substituent. X ²¹ to X ³⁰ each independently represent a sulfur atom, an oxygen atom or a selenium atom. ]

The substituent represented by R ²¹ to R ⁴² may, for example, be a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aryl group, an aryloxy group, Arylthio, aralkyl, aralkyloxy, aralkylthio, aralkenyl, arylalkynyl, amine, substituted amine, fluorenyl, substituted fluorenyl, fluorenyl, decyloxy, decylamino And a heterocyclic group, a carboxyl group which may have a substituent, a nitro group, and a cyano group.

R ²¹ , R ²² and R ^{35 are} preferably an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an alkylthio group which may have a substituent, and may have an alkyl group which may have a substituent and may have a substituent The alkoxy group is preferred, and the alkyl group which may have a substituent is more preferred. In order to improve the solubility of the polymer compound of the present invention, R ²¹ , R ²² , R ³⁵ , R ³⁹ and R ^{42 are} preferably a branched alkyl group.

R ²³ , R ²⁴ , R ²⁷ , R ²⁸ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁷ , R ³⁸ , R ⁴⁰ and R ^{41 are} preferably a halogen atom and a hydrogen atom, and have a fluorine atom and a hydrogen atom. Preferably, the hydrogen atom is more preferred.

R ²⁵ , R ²⁶ , R ²⁹ and R ^{30 are} preferably a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group and an aralkyl group, and more preferably a hydrogen atom or an aralkyl group.

R ^{36 is} preferably a hydrogen atom, a halogen atom, a fluorenyl group or a decyloxy group, and more preferably a fluorenyl group or a decyloxy group.

X ²¹ to X ³⁰ each independently represent a sulfur atom, an oxygen atom or a selenium atom. However, in order to increase the short-circuit current density of the photoelectric conversion element of the present invention, it is preferably a sulfur atom and an oxygen atom, and a sulfur atom is preferred.

In the present invention, in order to increase the short-circuit current density of the photoelectric conversion element, the polymer compound preferably has the formula (2-1), the formula (2-2), the formula (2-3) or the formula (2-10). The structural unit is preferably a structural unit represented by the formula (2-1), the formula (2-2) or the formula (2-10), and has a formula (2-1) or a formula (2-10). The structural unit is better, and the knot represented by the formula (2-10) The unit of construction is particularly good.

Meanwhile, the polymer compound having the structural unit represented by the formula (1) may be a polymer compound further comprising a structural unit represented by the formula (2).

[wherein, X ¹ and X ^{2 are the} same or different and represent a nitrogen atom or =CH-. Y ¹ represents a sulfur atom, an oxygen atom, a selenium atom, -N(R ⁴³ )- or -CR ⁴⁴ =CR ⁴⁵ -. R ⁴³ , R ⁴⁴ and R ^{45 are the} same or different and each represents a hydrogen atom or a substituent. W ¹ and W ^{2 are the} same or different and each represents a cyano group, a monovalent organic group having a fluorine atom, a halogen atom or a hydrogen atom. ]

In the formula (2), although X ¹ and X ² represent a nitrogen atom or =CH-, it is preferred that at least one of X ¹ and X ² is a nitrogen atom, and it is preferred that both of X ¹ and X ² are nitrogen atoms. .

In the formula (2), the monovalent organic group having a fluorine atom represented by W ¹ and W ² may, for example, be a fluoroaryl group, a fluoroalkyl group, a fluoroalkylthio group, a fluorosulfonyl group or a fluoroethenyl group. The fluoroalkyl group may, for example, be a fluoromethyl group. Examples of the fluoroaryl group include a fluorophenyl group and the like. In this case, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In terms of the absorption strength and solubility of the polymer compound containing the structural unit represented by the formula (2), W ¹ and W ^{2 are} preferably a fluorine atom.

In the formula (2), Y ¹ represents a sulfur atom, an oxygen atom, a selenium atom, -N(R ⁴⁶ )- or -CR ⁴⁷ =CR ⁴⁸ -, and R ⁴⁶ , R ⁴⁷ and R ^{48 are the} same or different and represent a hydrogen atom. , a halogen atom or a substituent. In this case, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkyloxy group, an aralkylthio group, an anthranyl group, and an anthracene group. Oxyl, decylamino, quinone imine, imine, amine, substituted amine, substituted fluorenyl, substituted methoxy, substituted thiol, substituted fluorenyl, monovalent heterocyclic, heterocyclic Oxy, heterocyclic thio, aralkenyl, aralkynyl, carboxy, cyano.

In terms of the absorption strength and solubility of the polymer compound containing the structural unit represented by the formula (1), Y ^{1 is} preferably a sulfur atom or an oxygen atom.

In the present invention, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the present invention, the alkyl group may be linear or branched, or may be cyclic. The carbon number of the alkyl group is usually from 1 to 30. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a n-pentyl group, and an isopentyl group. 2-methylbutyl, 1-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, heptyl, octyl, isooctyl , 2-ethylhexyl, 3,7-dimethyloctyl, decyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, twentieth A chain alkyl group such as an alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or an adamantyl group.

In the present invention, the alkoxy group may be linear or branched, or may be cyclic. The carbon number of the alkoxy group is usually from 1 to 20. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a third butoxy group, a pentyloxy group, and a hexyloxy group. , cyclohexyloxy, heptyloxy, Octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, 3,7-dimethyloctyloxy, dodecyloxy. Specific examples of the substituted alkoxy group include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, a perfluorooctyloxy group, and a methoxymethyloxy group. And a fluoroalkoxy group having 1 to 20 carbon atoms such as 2-methoxyethyloxy group.

In the present invention, the alkylthio group may be linear or branched, or may be a cycloalkylthio group. The carbon number of the alkylthio group is usually from 1 to 20, and specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, and Isobutylthio, tert-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, 2-ethylhexylthio, decylthio, Mercaptothio, 3,7-dimethyloctylthio, dodecylthio, trioxymethylthio.

The aryl group in the present invention usually has a carbon number of 6 to 60. Specific examples of the aryl group include a phenyl group and a C1 to C12 alkoxyphenyl group (the C1 to C12 alkyl group represents an alkyl group having 1 to 12 carbon atoms. The C1 to C12 alkyl group is preferably a C1 to C8 alkyl group, and Preferred is a C1 to C6 alkyl group. The C1 to C8 alkyl group represents an alkyl group having 1 to 8 carbon atoms, and the C1 to C6 alkyl group represents an alkyl group having 1 to 6 carbon atoms. As a C1 to C12 alkyl group, a C1 to C8 alkane Specific examples of the group and the C1 to C6 alkyl group include the exemplified groups described in the above alkyl group. The following are also the same.), C1 to C12 alkylphenyl group, 1-naphthyl group, 2-naphthyl group, pentafluoro group Phenyl.

The aryloxy group in the present invention usually has a carbon number of 6 to 60. Specific examples of the aryloxy group include a phenoxy group, a C1 to C12 alkoxyphenoxy group, a C1 to C12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenoxy group. .

The arylthio group in the present invention usually has a carbon number of 6 to 60. As aromatic sulfur Specific examples of the group include a phenylthio group, a C1 to C12 alkoxyphenylthio group, a C1 to C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a substituted arylthio group. Specific examples include a pentafluorophenylthio group.

The aralkyl group in the present invention usually has a carbon number of 7 to 60. Specific examples of the aralkyl group include a phenyl-C1 to C12 alkyl group, a C1 to C12 alkoxyphenyl-C1 to C12 alkyl group, a C1 to C12 alkylphenyl-C1 to C12 alkyl group, and 1- Naphthyl-C1 to C12 alkyl, 2-naphthyl-C1 to C12 alkyl.

The arylalkoxy group in the present invention usually has a carbon number of from 7 to 60. Specific examples of the arylalkoxy group include a phenyl-C1 to C12 alkoxy group, a C1 to C12 alkoxyphenyl-C1 to C12 alkoxy group, and a C1 to C12 alkylphenyl-C1 to C12 alkoxy group. Base, 1-naphthyl-C1 to C12 alkoxy, 2-naphthyl-C1 to C12 alkoxy.

The arylalkylthio group in the present invention usually has a carbon number of 7 to 60. Specific examples of the arylalkylthio group include a phenyl-C1 to C12 alkylthio group, a C1 to C12 alkoxyphenyl-C1 to C12 alkylthio group, and a C1 to C12 alkylphenyl-C1 to C12 alkyl sulfide. Base, 1-naphthyl-C1 to C12 alkylthio, 2-naphthyl-C1 to C12 alkylthio.

The fluorenyl group in the present invention usually has a carbon number of 2 to 20. Specific examples of the fluorenyl group include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a trimethyl ethane group, a benzamidine group, a trifluoroethyl fluorenyl group, and a pentafluorobenzyl fluorenyl group.

The decyloxy group in the present invention usually has a carbon number of 2 to 20. Specific examples of the decyloxy group include an ethoxycarbonyl group, a propenyloxy group, a butoxy group, an isobutyloxy group, a trimethyl ethoxy group, a benzyl group, and a trifluoroacetic acid. Oxyl, pentafluorobenzylideneoxy.

The carbon number of the guanamine group is usually from 1 to 20. The guanamine group refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from a guanamine. Specific examples of the guanamine group include a formamidine group, an acetamino group, a propylamine group, a butylammonium group, a benzammonium group, a trifluoroacetamido group, and a pentafluorobenzamide. Base, dimethylamino, diethylamine, dipropylamine, dibutylammonium, benzoylamino, di-trifluoroacetamido, bis-pentafluorobenzamide base.

The quinone imine group in the present invention means a group obtained by removing a hydrogen atom bonded to a nitrogen atom from a quinone imine. Specific examples of the quinone imine group include an amber quinone imine group and a quinone imine group.

The substituted amine group in the present invention usually has a carbon number of from 1 to 40. Specific examples of the substituted amine group include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a propylamino group, a dipropylamino group, an isopropylamino group, Diisopropylamino, butylamino, isobutylamino, tert-butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2 -ethylhexylamino, decylamino, decylamino, 3,7-dimethyloctylamino, dodecylamino, cyclopentylamino, dicyclopentylamino, ring Hexylamino, dicyclohexylamino, pyrrolidinyl, piperidinyl, di-trifluoromethylamino, phenylamino, diphenylamino, C1 to C12 alkoxyphenylamino, di C1 to C12 alkoxyphenyl)amino, di(C1 to C12 alkylphenyl)amine, 1-naphthylamino, 2-naphthylamino, pentafluorophenylamino, pyridylamino, hydrazine Azinylamino, pyrimidinylamino, pyrazinylamino, triazinylamino, phenyl-C1 to C12 alkylamino, C1 to C12 alkoxyphenyl-C1 to C12 alkylamino, C1 To C12 alkylphenyl-C1 to C12 alkylamino group, di(C1 to C12 alkoxyphenyl-C1 to C12 alkyl)amino group, di(C1 to C12 alkane) Phenyl-C1 to C12 alkyl)amino, 1-naphthyl-C1 to C12 alkylamino, 2-naphthyl-C1 to C12 alkylamino.

The substituted fluorenyl group in the present invention may, for example, be a trimethyl fluorenyl group, a triethyl decyl group, a tri-n-propyl fluorenyl group, a triisopropyl fluorenyl group, a tert-butyldimethyl fluorenyl group or a triphenyl group. A fluorenyl group, a tri-p-dimethylphenyl fluorenyl group, a tribenzyl fluorenyl group, a diphenylmethyl fluorenyl group, a tert-butyldiphenyl fluorenyl group, a dimethylphenyl fluorenyl group.

The substituted methoxy group in the present invention may, for example, be a trimethyl decyloxy group, a triethyl decyloxy group, a tri-n-propyl decyloxy group, a triisopropyl decyloxy group or a tert-butyldimethyl group. Anthraceneoxy, triphenylphosphoniumoxy, tri-p-xylyloxyloxy, tribenzylphosphoniumoxy, diphenylmethyldecyloxy, tert-butyldiphenylphosphonium, two Methylphenyl decyloxy.

The substituted thiol group in the present invention may, for example, be a trimethylsulfoniumthio group, a triethylsulfoniumthio group, a tri-n-propylsulfonylthio group, a triisopropylsulfoniumthio group or a tert-butyldimethyl group. Sulfhydryl, triphenylsulfonylthio, tri-p-dimethylphenylsulfonylthio, tribenzylsulfonylthio, diphenylmethylsulfonylthio, tert-butyldiphenylsulfonylthio, Methylphenyl sulfonylthio.

The substituted guanamine group in the present invention may, for example, be a trimethylammonium group, a triethylammonium group, a tri-n-propylammonium group, a triisopropylammonium group or a tert-butyldimethyl group. Amidino, triphenylguanamine, tris-p-dimethylphenylguanamine, tribenzylammonium, diphenylmethylguanamine, tert-butyldiphenylnonylamine, Methylphenyl decylamino, bis(trimethyldecyl)amine, bis(triethyldecyl)amine, bis(tri-n-propylmercapto)amine, bis(triisopropyldecyl) Amino, bis(tert-butyldimethylmethyl)amino, bis(triphenylindenyl)amino, bis(tri-p-dimethylphenyl)amino, di(tribenzyl)矽 Amino group, bis(diphenylmethylhydrazino)amino group, bis(t-butyldiphenylfluorenyl)amino group, bis(dimethylphenylindenyl)amino group.

The monovalent heterocyclic group in the present invention may, for example, be furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, Pyrazole, pyrazoline, pyrazolidine, furazan, triazole, thiadiazole, oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine , pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, anthracene, isoindole, pyridazine, indoline, isoindoline , chromene, chromane, isochroman, benzopyran, quinoline, isoquinoline, quinolizine, benzimidazole, benzothiazole, carbazole, naphthyridine, quinacrid Porphyrin, quinazoline, quinazolidine, cinnoline, phthalazine, guanidine, pteridine, oxazole, xanthene, phenanthridine, acridine, β-carboline (β- Removal of 1 hydrogen atom from a heterocyclic compound such as carboline), perimidine, phenanthroline, thiazolidine, phenoxathiin, phenoxazine, phenothiazine, phenazine After the base. The monovalent heterocyclic group is preferably a monovalent aromatic heterocyclic group.

The heterocyclic oxy group in the present invention is a group represented by the formula (4) in which an oxygen atom is bonded to the above monovalent heterocyclic group. The heterocyclic thio group includes a group represented by the formula (5) in which a sulfur atom is bonded to the above monovalent heterocyclic group.

In the formulae (4) and (5), Ar ⁷ represents a monovalent heterocyclic group.

The heterocyclic oxy group in the present invention usually has a carbon number of from 2 to 60. Specific examples of the heterocyclic oxy group include a thienyloxy group, a C1 to C12 alkylthiophenoxy group, a pyrroloxy group, a furyloxy group, a pyridyloxy group, a C1 to C12 alkylpyridyloxy group, an imidazolyl group, and the like. Pyrazolyloxy, triazolyloxy, oxazolyloxy, thiazolyloxy, thiadiazolyloxy.

The heterocyclic thio group in the present invention usually has a carbon number of from 2 to 60. Specific examples of the heterocyclic fluorenyl group include a thiophene fluorenyl group, a C1 to C12 alkylthiophene fluorenyl group, a pyrrolidinyl group, a furyl fluorenyl group, a pyridinium group, a C1 to C12 alkylpyridinium group, an imidazolium group, a pyrazolyl group, a triazolium group, Oxazolyl, thiazolyl, thiadiazolyl.

The aralkenyl group in the present invention usually has a carbon number of 8 to 20, and specific examples of the arylalkenyl group include a styryl group.

The aralkynyl group in the present invention usually has a carbon number of 8 to 20. Specific examples of the aralkynyl group include a phenylethynyl group.

The structural unit represented by the formula (2) is preferably a structural unit represented by the formula (2-11) and a structural unit represented by the formula (2-12).

The polymer compound of the present invention may contain a structural unit represented by the formula (2') in addition to the structural unit represented by the formula (1).

[In the formula, Ar ³ represents an extended aryl group different from the structural unit represented by the formula (1) or a heteroaryl group different from the structural unit represented by the formula (1). ]

The extended aryl group in the present invention may, for example, be a phenylene group, a naphthalenediyl group, a fluorenyldiyl group, a pyrenediyl group or a fluorenyldiyl group. The heteroaryl group may, for example, be a furanyl group, a pyrrole diyl group or a pyridyldiyl group.

A preferred form of the structural unit represented by the formula (1) is a group represented by the formula (3).

In the formula (3), Ar ¹¹ and Ar ^{21 are the} same or different and each represents a trivalent heterocyclic group. X ³ represents -O-, -S-, -C(=O), -S(=O)-, -SO ₂ -, -Si(R ⁹ )(R ⁴ )-, -N(R ⁵ )- , -B(R ⁶ )-, -P(R ⁷ )- or -P(=O)(R ⁸ )-.

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are the} same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group or an arylthio group. , aralkyl, aralkyloxy, aralkylthio, fluorenyl, decyloxy, decylamino, fluorenylene, imido, amine, substituted amine, substituted fluorenyl, substituted methoxy And a substituted thiol group, a substituted guanylamino group, a monovalent heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an aralkenyl group, an arylalkynyl group, a carboxyl group or a cyano group. R ⁵⁰ and R ^{51 are the} same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkyloxy group or an aralkyl group. Thio, fluorenyl, decyloxy, decylamino, fluorenylene, imido, amine, substituted amine, substituted fluorenyl, substituted methoxy, substituted thiol, substituted guanylamine, 1 A heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an aralkenyl group, an aralkynyl group, a carboxy group or a cyano group. X ³ and Ar ²¹ are adjacent to each other in the hetero ring contained in Ar ¹¹ , and C(R ⁵⁰ )(R ⁵¹ ) and Ar ¹¹ are bonded to adjacent positions of the hetero ring contained in Ar ²¹ .

In the formula (3), Ar ¹¹ and Ar ^{21 are the} same or different and each represents a trivalent heterocyclic group.

The trivalent heterocyclic group refers to an atomic group remaining after removing three hydrogen atoms from the heterocyclic compound.

The heterocyclic compound herein refers to an organic compound having a ring structure, and the element constituting the ring is not only a carbon atom but also a hetero atom such as oxygen, sulfur, nitrogen, phosphorus or boron.

The trivalent heterocyclic group may, for example, be the following one.

In the formulae (201) to (284), R' is the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or an aralkyl group. , aralkyloxy, aralkylthio, substituted amine, decyloxy, decylamino, aralkenyl, aralkynyl, monovalent heterocyclic or cyano.

R" identical or different means hydrogen atom, alkyl group, aryl group, aralkyl group, Substituting fluorenyl, fluorenyl or monovalent heterocyclic groups.

In the formula (3), at least one of Ar ¹¹ and Ar ²¹ is preferably a group in which three hydrogen atoms are removed from the thiophene ring, and a group in which three hydrogen atoms are simultaneously removed from the thiophene ring is preferred.

Meanwhile, in the formulae (201) to (284), the trivalent heterocyclic group is preferably a heterocyclic group containing a sulfur atom, and a group represented by the formula (268) or the formula (273) is preferred, and 273) The base represented is better.

R ⁵⁰ and R ^{51 are} preferably an alkyl group having 6 or more carbon atoms, an alkoxy group having 6 or more carbon atoms, an alkylthio group having 6 or more carbon atoms, an aryl group having 6 or more carbon atoms, or carbon, which are the same or different from each other. An aryloxy group having 6 or more, an arylthio group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, an aralkyloxy group having 7 or more carbon atoms, an aralkylthio group having 7 or more carbon atoms, or a carbon number of 6 or more A mercapto group or a decyloxy group having 6 or more carbon atoms, and an alkyl group having 6 or more carbon atoms, an alkoxy group having 6 or more carbon atoms, an aryl group having 6 or more carbon atoms, and an aryloxy group having 6 or more carbon atoms are more preferable. Further, an alkyl group having a carbon number of 6 or more is particularly preferable.

As the polymer compound having a structural unit represented by the formula (1), for example, the polymer compound A can be exemplified.

The polymer compound A has the following repeating unit. Where n represents the number of repeating units.

The polymer compound containing the structural unit represented by the formula (1) may be contained in the active layer as an electron-donating compound, and may be contained in the active layer as an electron-accepting compound, but is preferably contained in the active layer as an electron supply. Sex compounds.

As the electron-donating compound, in addition to the polymer compound containing the structural unit represented by the formula (1), for example, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, or a triphenyldiamine may also be mentioned. Derivatives, oligothiophenes and derivatives thereof, polyvinyl carbazole and its derivatives, polydecane and its derivatives, polyoxyalkylene derivatives having aromatic amine residues in the side chain or main chain, polyaniline and Derivatives, polythiophenes and derivatives thereof, polypyrrole and its derivatives, polyphenylethylene and its derivatives, polythiophene ethylene and its derivatives. Among these compounds, oligothiophene and a derivative thereof, and a polymer compound containing a structural unit represented by the formula (1) are preferable, and poly(3-hexylthiophene) (P3HT) is preferable. Further, in terms of improving the photoelectric conversion efficiency, it is preferably a polymer compound having a structural unit represented by the formulae (2-1) to (2-10).

The electron-donating compound can be used alone in the active layer or 2 The above combination is used in the active layer.

Examples of the electron accepting compound include oxadiazole derivatives, quinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, hydrazine and its derivatives, and tetracyanoquinone. Dimethane and its derivatives, anthrone derivatives, diphenyldicyanoethylene and its derivatives, diphenolphthalein derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and Derivatives, polyquinoxalines and their derivatives, polyfluorene and its derivatives, fullerene such as C ₆₀ and its derivatives, 2,9-dimethyl-4,7-diphenyl-1,10 a phenanthrene derivative such as bathocuproine, a metal oxide such as titanium oxide, or a carbon nanotube. As the electron accepting compound, titanium oxide, a carbon nanotube, a fullerene, and a fullerene derivative are preferable, and a fullerene or a fullerene derivative is particularly preferable. A fullerene derivative, which represents at least a portion of a modified compound of a fullerene.

Examples of the fullerene include C ₆₀ fullerene, C ₇₀ fullerene, C ₇₆ fullerene, C ₇₈ fullerene, C ₈₄ fullerene, and the like.

The fullerene derivative may, for example, be a compound represented by the formula (6), a compound represented by the formula (7), a compound represented by the formula (8) or a compound represented by the formula (9).

In the formulae (6) to (9), R ^a is an alkyl group, an aryl group, a heteroaryl group or a group having an ester structure. A plurality of R ^a may be the same or different. R ^b represents an alkyl group or an aryl group. A plurality of R ^b may be the same or different.

The group having an ester structure represented by R ^a may, for example, be a group represented by the formula (10).

(wherein, u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and R ^c represents an alkyl group, an aryl group or a heteroaryl group.)

Specific examples of the heteroaryl group in the present invention include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.

Examples of the fullerene and fullerene derivatives include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ and derivatives thereof. Examples of the derivative of C ₆₀ fullerene and the derivative of C ₇₀ fullerene include the following compounds.

Meanwhile, as an example of the fullerene derivative, methyl [5,6]-phenyl C61 butyrate ([5,6]-PCBM), methyl [6,6]-phenyl C61 butyrate (C60PCBM, [6,6]-phenyl C61 butyric acid methyl ester), [6,6]-phenyl C71 butyric acid methyl ester (C70PCBM, [6,6]-phenyl C71 butyric acid methyl ester), [6, 6]-Phenyl C85 butyric acid methyl ester (C84PCBM, [6,6]-phenyl C85 butyric acid methyl Ester), [6,6]-thienyl C61 butyric acid methyl ester (such as [6,6]-thienyl C61 butyric acid methyl ester).

When the active layer contains an electron-donating compound and a fullerene derivative, the amount of the fullerene derivative in the active layer is preferably from 10 to 1,000 parts by weight and from 20 to 500 with respect to 100 parts by weight of the electron-donating compound. The parts by weight are preferred.

The electron-accepting compound may be used in one active compound in the active layer, or two or more kinds of compounds may be combined and used in the active layer.

In the present invention, the active layer of the organic photoelectric conversion device is formed of a liquid containing a polymer compound and a fluorine-containing solvent. A solvent containing no fluorine atom may also be mixed in the liquid.

The fluorine-containing solvent may be a solvent containing a fluorine atom in the molecule, and is preferably a solvent having two or more fluorine atoms in one molecule. The fluorine-containing solvent is preferably contained in the form of 5 or more fluorine atoms, more preferably 7 or more, and particularly preferably 9 or more. The fluorine-containing solvent may, for example, be CF ₃ CF ₂ CHCl ₂ , CClF ₂ CF ₂ CHClF, CF ₃ CH ₂ OCF ₂ CHF ₂ , C ₃ F ₇ OCH ₃ , C ₄ F ₉ OCH ₃ or C ₄ F ₉ OC _{2 .} H ₅ , C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ , C ₃ HF ₆ -CH(CH ₃ )OC ₃ HF ₆ . ASUSIKLIN AK-225* (CF ₃ CF ₂ CHCl ₂ /CClF ₂ CF ₂ CHClF) manufactured by Asahi Glass Co., Ltd., ASAHIKLIN AK-225AES, ASAHIKLIN AE-3000 (CF ₃ CH ₂ OCF ₂ CHF ₂ ) can also be used. , AE-3100E, Suve 3M made by Novec7000 (C ₃ F ₇ OCH ₃ ), Novec 7100 (C ₄ F ₉ OCH ₃ ), Novec 7200 (C ₄ F ₉ OC ₂ H ₅ ), Novec 7300 (C ₂ F ₅ CF (OCH) ₃ ) C ₃ F ₇ ), Novec 7600 (C ₃ HF ₆ -CH(CH ₃ )OC ₃ HF ₆ ). The fluorine-containing solvent may also be mixed with a solvent containing no fluorine atom to adjust the boiling point, viscosity, surface tension, and the like.

The solvent containing no fluorine atom is suitably selected from water and an organic solvent depending on the type of the electron-donating compound and the electron-accepting compound. Examples of the organic solvent include toluene, xylene, mesitylene, tetrahydronaphthalene, decahydronaphthalene, dicyclohexane, n-butylbenzene, t-butylbenzene, and t-butylbenzene. Saturated hydrocarbon solvent, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromine A halogenated saturated hydrocarbon solvent such as cyclohexane, a halogenated unsaturated hydrocarbon solvent such as chlorobenzene, dichlorobenzene or trichlorobenzene, or an ether solvent such as tetrahydrofuran or tetrahydropyran. Among these solvents, a halogenated unsaturated hydrocarbon solvent is preferred, and dichlorobenzene is preferred, and o-dichlorobenzene is more preferred.

The amount of the fluorine-containing solvent in the liquid containing the polymer compound and the fluorine-containing solvent is not particularly limited, and is usually from 99.9 wt% to 0.001 wt%, and preferably from 50 wt% to 0.01 wt%, to 30 wt%. From 0.01 to 0.05% by weight is preferred, and from 15% by weight to 0.1% by weight is particularly preferred.

The amount of the polymer compound in the liquid containing the polymer compound and the fluorine-containing solvent is not particularly limited, and may be appropriately selected from the range of 0.1% by weight to 10% by weight, and preferably 0.3% by weight or more. It is preferably 5% by weight or less and preferably 3% by weight or less.

a liquid containing a polymer compound and a fluorine-containing solvent, such as an electron-accepting compound and an electron-donating compound which is a polymer compound, the total amount of the electron-donating compound in the liquid and the amount of the electron-accepting compound, It is usually 0.2% by weight or more and 20% by weight or less, and preferably 0.5% by weight or more and 10% by weight or less, and 1% by weight or more and 5% by weight or less. The next is better. Meanwhile, the compounding ratio of the electron-donating compound to the electron-accepting compound is usually from 1 to 20:20 to 1, and preferably from 1 to 10:10 to 1, and preferably from 1 to 5:5 to 1. When the solution of the electron-donating compound and the electron-accepting compound are separately prepared, the electron-donating compound or the electron-accepting compound may be added in an amount of usually 0.4% by weight or more, and preferably 0.6% by weight or more, and 2% by weight. The above is preferred.

The liquid containing the polymer compound and the fluorine-containing solvent is preferably a liquid containing a polymer compound having a structural unit represented by the formula (1) and a fluorine-containing solvent.

An aspect of the method for producing an organic photoelectric conversion device of the present invention is a method for producing an organic photoelectric conversion element comprising a pair of electrodes and an active layer between the pair of electrodes, wherein the coating is contained on one of the electrodes a step of forming a living layer of a molecular compound and a solvent of a fluorine-containing solvent, and a method of producing a step of forming another electrode on the active layer.

The coating method may, for example, be a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a strip coating method, a roll coating method, a bar coating method, a dip coating method, a spray coating method, or a screen printing method. Method, gravure printing method, flexographic printing method, offset printing method, inkjet printing method, disperser printing method, nozzle coating method, capillary coating method, and the like. Among them, a spin coating method, a flexographic printing method, a gravure printing method, an inkjet printing method, and a disperser printing method are preferable, and a spin coating method is preferred.

When the organic photoelectric conversion element in which the active layer is a bulk heterojunction type is to be produced, for example, a solution containing both an electron-donating compound and an electron-accepting compound may be subjected to ultrasonic treatment at a frequency different from twice or more, and then processed. After the solution is coated on the electrode, the solvent is volatilized to form an activity. Floor.

On the other hand, when an organic photoelectric conversion element in which the active layer is a pn heterojunction type is to be produced, for example, a solution containing an electron-donating compound and a solution containing an electron-accepting compound may be subjected to ultrasonic waves of different frequencies twice or more. After the treatment, the treated solution containing the electron-donating compound is applied onto the electrode to volatilize the solvent to form an electron-donating layer. Next, a solution containing the treated electron-accepting compound is applied onto the electron-donating layer to volatilize the solvent to form an electron-accepting layer. Thus, an active layer composed of two layers can be formed. The order in which the electron supply layer and the electron accepting layer are formed may also be reversed from the above.

The thickness of the active layer is usually from 1 nm to 100 μm, and preferably from 2 nm to 1,000 nm, and preferably from 5 nm to 500 nm, more preferably from 20 nm to 200 nm.

The substrate may be any chemical change as long as it forms an electrode and forms an organic layer. Examples of the material of the substrate include glass, plastic, polymer film, fluorenone, and the like. In the case of an opaque substrate, it is preferred that the opposite electrode (i.e., the electrode of the pair of electrodes that is further away from the substrate) be transparent or translucent.

Examples of the electrode material constituting the transparent or translucent electrode include a conductive metal oxide film, a translucent metal film, and the like. Specifically, indium oxide, zinc oxide, tin oxide, and the like of indium may be used. tin. Oxide (ITO), indium. Zinc. A film made of a conductive material such as oxide (IZO) or NESA, or a metal film such as gold, platinum, silver or copper, and ITO or indium is preferably used. Zinc. A film made of a conductive material formed of an oxide, tin oxide, or the like. As for the method of producing the electrode, for example, a vacuum evaporation method, a sputtering method, Ion plating method, electroplating method, and the like. Meanwhile, as the electrode material, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof can also be used.

Electrodes that do not require transparent or translucent electrodes may be transparent or translucent, or opaque or non-translucent. As the electrode material constituting the electrode, a metal, a conductive polymer or the like can be used. Specific examples of the electrode material include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, strontium, vanadium, zinc, bismuth, indium, bismuth, antimony, bismuth, antimony, bismuth. Or a metal; an alloy of two or more of the foregoing metals; and one or more of the foregoing metals and a group selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin Alloys of the above metals; graphite, graphite intercalation compounds; polyaniline and its derivatives, polythiophene and its derivatives. Examples of the alloy include a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, and a calcium-aluminum alloy.

Examples of the material of the intermediate layer include halides or oxides of alkali metals or alkaline earth metals such as lithium fluoride (LiF), fine particles of inorganic semiconductors such as titanium oxide, metal alkoxides, and PEDOT (poly(3,4) ethylene). Dioxythiophene). Among these materials, the intermediate layer on the anode side should preferably be a layer formed by PEDOT. The intermediate layer on the cathode side is preferably a layer formed of an alkali metal halide (preferably LiF) or a titanium oxide thin film layer formed of titanium isopropoxide, and a layer formed of lithium fluoride (LiF), titanium A titanium oxide thin film layer formed of propoxide is preferred.

The organic photoelectric conversion element manufactured by the production method of the present invention can emit light from a transparent or translucent electrode by light such as sunlight, and can function as an organic thin film solar cell. also may A plurality of organic thin film solar cells are accumulated and used as an organic thin film solar cell module.

Meanwhile, in a state where a voltage is applied between electrodes or a state where no voltage is applied, light may be irradiated onto a transparent or translucent electrode to cause a photocurrent to flow to function as an organic photosensor. A plurality of organic light sensors can also be used as an organic image sensor after being accumulated.

The organic thin film solar cell basically has the same module structure as the conventional solar cell module. In a solar cell module, a battery is generally formed on a support substrate such as a metal or a ceramic, and then a resin or a protective glass is coated thereon to form a light-receiving structure on the opposite side of the support substrate, but it may be on the support substrate. A transparent material such as tempered glass is used, and after the battery is formed thereon, a structure in which light is taken out from the side of the transparent supporting substrate is formed. Specifically, a substrate structure called a super straight type, a substraight type, a potting type, an amorphous fluorenone solar cell, or the like is known. Module structure and so on. The organic thin film solar cell of the present invention can also be suitably selected according to the purpose of use, the place of use, and the environment.

A representative ultra-straight or sub-straight module is a battery that is disposed at a certain interval between support substrates that are transparent on one side or both sides and that are subjected to anti-reflection treatment. A wire or a flexible wire or the like is connected, and a collector electrode is disposed on the outer edge portion to form a structure that can take out generated electric power. A plastic film or a variety of plastic materials such as ethylene vinyl acetate (EVA) in a resin form may be used between the substrate and the battery to improve the protection or collection efficiency of the battery. At the same time, as When the hard material is not required to be coated to reduce the external impact, the surface protective layer is formed of a transparent plastic film, or the filling resin is cured to provide a protective function, and the support substrate on one side may not be used. The periphery of the support substrate is fixed in a sandwich shape by a metal frame to ensure the internal seal and the rigidity of the module, and is sealed with a sealing material between the support substrate and the frame. At the same time, a solar cell can be formed on the curved surface as long as a flexible material is used for the battery body or the support substrate, the filling material, and the sealing material.

When a solar cell using a flexible support such as a polymer film is used, the battery is sequentially formed by feeding the roll-shaped support, and the battery is cut to a desired size, and the peripheral portion is bendable and prevented. The wet material is sealed to make the battery body. At the same time, it can also be used as a module structure called "SCAF" described in Solar Energy Materials and Solar Cells, 48, p383-391. Further, the solar cell using the flexible support may be used by being fixed to a curved glass or the like.

When there is an insoluble component or dust in the solution at the time of film formation, chipping will occur on the coating film, and at the same time, non-essential components or dust may be nucleated to generate agglomerated particles. Therefore, the electrical and chemical contact of the joint interface is poor, or leakage occurs. By reducing these conditions, the photoelectric conversion efficiency can be improved.

[Examples] Synthesis Example 1 (Synthesis of Compound 1)

To a 1,000-mL four-necked flask in which the gas in the flask was replaced with argon, 13.0 g (80.0 mmol) of 3-bromothiophene and 80 mL of diethyl ether were added to make a homogeneous solution. The solution was maintained at -78 ° C, and 31 mL (80.6 mmol) of a 2.6 M solution of n-butyllithium (n-BuLi) in hexane was added dropwise. After reacting at -78 ° C for 2 hours, a solution of 8.96 g (80.0 mmol) of 3-thiophene was dissolved in 20 mL of diethyl ether. After dripping, it was stirred at -78 ° C for 30 minutes and further stirred at room temperature (25 ° C) for 30 minutes. The reaction solution was again cooled to -78 ° C, and 2.6 M of a hexane solution of n-BuLi (62 mL) (161 mmol) was dropped over 15 minutes. After the dropwise addition, the reaction solution was stirred at -25 ° C for 2 hours, and further stirred at room temperature (25 ° C) for 1 hour. Then, the reaction liquid was cooled to -25 ° C, and a solution in which 60 g (236 mmol) of iodine was dissolved in 1,000 mL of diethyl ether was dropped over 30 minutes. After the dropwise addition, the mixture was stirred at room temperature (25 ° C) for 2 hours, and 50 mL of a 1 N aqueous sodium thiosulfate solution was added thereto to terminate the reaction. After extracting the reaction product with diethyl ether, the reaction product was dried over magnesium sulfate. After filtration, the filtrate was concentrated to give 35 g of crude product. The crude product was recrystallized and purified using chloroform to obtain 28 g of Compound 1.

(Synthesis of Compound 2)

In a 300 mL four-necked flask, 10.5 g (23.4 mmol) of diiodothiophene methanol (Compound 1) and 150 mL of dichloromethane were added to make a homogeneous solution. After 7.50 g (34.8 mmol) of pyridinium chlorochromate was added to the solution, the mixture was stirred at room temperature (25 ° C) for 10 hours. After filtering the reaction liquid and removing the insoluble matter, the filtrate was concentrated to obtain 10.0 g (22.4 mmol) of Compound 2.

(Synthesis of Compound 3)

In a 300 mL flask in which the gas in the flask was replaced with argon, 10.0 g (22.4 mmol) of the compound 2, copper powder 6.0 g (94.5 mmol), and dehydrated N,N-dimethylformamide (hereinafter referred to as DMF) were added. 120 mL, stirred at 120 ° C for 4 hours. After the reaction, the flask was cooled to room temperature (25 ° C), and the reaction liquid was passed through a gel column to remove insoluble components. Then, 500 mL of water was added, and the reaction product was extracted with chloroform. After the oil layer of the chloroform solution was dried over magnesium sulfate, the oil layer was filtered, and the filtrate was concentrated to give a crude product. This crude product was purified by a silica gel column in which a solvent was evaporated to afford 3.26 g of Compound 3. This operation is performed several times.

(Synthesis of Compound 4)

In a flask in which the gas in the flask was replaced with argon, 10.0 g (5.20 mmol) of Compound 3 and tetrahydrofuran (hereinafter also referred to as THF) (100 mL) were added to make a homogeneous solution. The flask was kept at 0 ° C, and 2.31 g (1.30 mmol) of N-bromosuccinimide (hereinafter also referred to as NBS) was added over 15 minutes. Then, the mixture was stirred at 0 ° C for 2 hours, and the precipitated solid was collected by filtration, and washed with a 10 wt% aqueous sodium thiosulfate solution and water. The resulting solid is referred to as crude 4-A. Then, 200 mL of a 10 wt% aqueous sodium thiosulfate solution was added to the filtrate, followed by extraction with chloroform. The organic layer of the chloroform solution was dried over sodium sulfate and filtered. The solid which precipitated the filtrate was collected and recovered. The resulting solid is referred to as crude 4-B. The crude product 4-A was mixed with the crude product 4-B, and purified by a silica gel column chromatography eluting with chloroform to afford 17.3 g of Compound 4. This operation is performed several times.

(Synthesis of Compound 5)

25.0 g (71.4 mmol) of compound 4, chloroform was placed in a 1,000 mL four-necked flask equipped with a mechanical stirrer and a gas in which the gas was replaced with argon. 250 mL and 160 mL of trifluoroacetic acid make it a homogeneous solution. 21.0 g (210 mmol) of sodium perborate monohydrate was added to the solution over 35 minutes, and the mixture was stirred at room temperature (25 ° C) for 240 minutes. Then, 500 mL of a 5 wt% aqueous sodium sulfite solution was added to the reaction liquid to stop the reaction, and then sodium hydrogencarbonate was added until the pH of the reaction liquid became 6. Then, the reaction product was extracted with chloroform, and the organic layer of the chloroform solution was passed through a silica gel column to obtain a filtrate, and the solvent of the filtrate was distilled off by an evaporator. The residue was recrystallized using methanol to give 7.70 g (21.0 mmol) of Compound 5. This operation is performed several times.

(Synthesis of Compound 6)

In a 2,000 mL flask in which the gas in the flask was replaced with argon, 23.1 g (63.1 mmol) of Compound 5 and 1,500 mL of THF were added to make a homogeneous solution. The flask was cooled to -50 ° C, and 1 mol/L of 190 mL of a solution of n-octylmagnesium bromide in THF was added dropwise over 10 minutes. After stirring the reaction solution at -50 ° C for 30 minutes, 500 mL of water was added to stop the reaction. The reaction solution was warmed to room temperature (25 ° C), and 1,000 mL of THF was distilled off with an evaporator, and then 100 mL of acetic acid was added. The reaction product was extracted with chloroform, and then the chloroform solution was dried over sodium sulfate. After filtering the chloroform solution, the solvent of the filtrate was distilled off with an evaporator. The obtained solid was washed with hexane and dried under reduced pressure to give 10.9 g of Compound 6.

(Synthesis of Compound 7)

To a 100 mL four-necked flask in which the gas in the flask was replaced with argon, 1.00 g (4.80 mmol) of Compound 6 and 30 mL of dehydrated THF were added to make a homogeneous solution. While maintaining the flask at -20 ° C, 12.7 mL of a 1 M solution of 3,7-dimethyloctylmagnesium bromide in ether was added. Then, the temperature of the reaction liquid was raised to -5 ° C over 30 minutes, and the mixture was stirred for 30 minutes. Then, the temperature of the reaction liquid was raised to 0 ° C over 10 minutes, and the mixture was stirred for 1.5 hours. Then, water was added to the reaction mixture to stop the reaction, and the reaction product was extracted with ethyl acetate. The organic layer was dried over sodium sulfate as an ethyl acetate solution. After filtration, the ethyl acetate solution was passed through a silica gel column, and the solvent of the filtrate was distilled off to obtain 1.50 g of Compound 7.

¹ H NMR in CDCl ₃ (ppm): 8.42 (b, 1H), 7.25 (d, 1H), 7.20 (d, 1H), 6.99 (d, 1H), 6.76 (d, 1H), 2.73 (b, 1H) ), 1.90 (m, 4H), 1.58-1.02 (b, 20H), 0.92 (s, 6H), 0.88 (s, 12H)

(Synthesis of Compound 8)

In a 200 mL flask in which the gas in the flask was replaced with argon, 1.50 g of Compound 7 and 30 mL of toluene were added to make a homogeneous solution. 100 mg of sodium p-toluenesulfonate monohydrate was added to the solution, and the mixture was stirred at 100 ° C for 1.5 hours. After cooling the reaction liquid to room temperature (25 ° C), 50 mL of water was added, and the reaction product was extracted with toluene. The organic layer was dried over sodium sulfate as a toluene solution, and after filtration, solvent was evaporated. The obtained crude product was purified by a ruthenium gel column in which a solvent was evaporated to afford 1.33 g of Compound 8. This operation is performed several times.

¹ H NMR in CDCl ₃ (ppm): 6.98 (d, 1H), 6.93 (d, 1H), 6.68 (d, 1H), 6.59 (d, 1H), 1.89 (m, 4H), 1.58-1.00 (b) , 20H), 0.87 (s, 6H), 0.86 (s, 12H)

(Synthesis of Compound 9)

In a 200 mL flask in which the gas in the flask was replaced with argon, 2.16 g (4.55 mmol) of the compound 8 and 100 mL of dehydrated THF were added to make A homogeneous solution. The solution was kept at -78 ° C, and 4.37 mL (11.4 mmol) of a 2.6 M solution of n-butyllithium in hexane was added dropwise to the solution over 10 minutes. After the dropwise addition, the reaction solution was stirred at -78 ° C for 30 minutes, and then stirred at room temperature (25 ° C) for 2 hours. Then, the flask was cooled to -78 ° C, and 4.07 g (12.5 mmol) of tributyltin chloride was added. After the addition, the mixture was stirred at -78 ° C for 30 minutes, and then stirred at room temperature (25 ° C) for 3 hours. Then, 200 mL of water was added to stop the reaction, and the reaction product was extracted with ethyl acetate. The organic layer was dried over sodium sulfate as an ethyl acetate solution. After filtration, the filtrate was concentrated with an evaporator and solvent was evaporated. The obtained oily substance was purified by a silica gel column in which a solvent was evaporated. The tannin in the silicone column was a silicone which was first impregnated with hexane containing 5 wt% of triethylamine for 5 minutes and then washed with hexane. After purification, 3.52 g (3.34 mmol) of Compound 9 was obtained.

Synthesis Example 2 (Synthesis of Compound 10)

In a 500 mL flask, 10.2 g (70.8 mmol) of 4,5-difluoro-1,2-diaminobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 mL of pyridine were added to make a homogeneous solution. The flask was kept at 0 ° C, and 16.0 g (134 mmol) of thiophene chloride was dropped into the flask. After the dropwise addition, the flask was kept at 25 ° C for 6 hours. Then, 250 mL of water was added, and the reaction product was extracted with chloroform. Sulfur The organic layer of the chloroform solution was dried over sodium sulfate and filtered. The filtrate was concentrated by an evaporator to recrystallize the precipitated solid. The solvent for recrystallization is methanol. After purification, 10.5 g (61.0 mmol) of Compound 10 was obtained.

¹ H NMR (CDCl ₃ , ppm): 7.75 (t, 2H)

¹⁹ F NMR (CDCl ₃ , ppm): -128.3 (s, 2F)

(Synthesis of Compound 11)

In a 100 mL flask, 2.00 g (11.6 mmol) of compound 10 and iron powder 0.20 g (3.58 mmol) were added, and the flask was heated to 90 °C. 31 g (194 mmol) of bromine was dropped into the flask over 1 hour. After dropping, it was stirred at 90 ° C for 38 hours. Then, the flask was cooled to room temperature (25 ° C), and then diluted with 100 mL of chloroform.

The obtained solution was poured into 300 mL of a 5 wt% aqueous sodium sulfite solution, and stirred for 1 hour. The organic layer of the obtained mixed liquid was separated by a separating funnel, and then the aqueous layer was extracted three times with chloroform. The resulting extract was mixed with the previously separated organic layer and dried over sodium sulfate. After filtration, the filtrate was concentrated with an evaporator and the solvent was evaporated. The obtained yellow solid was dissolved in 90 mL of methanol heated to 55 ° C, and then cooled to 25 ° C. The precipitated crystals were collected by filtration, and then dried under reduced pressure at room temperature (25 ° C) to yield 1.50 g of Compound 11.

¹⁹ F NMR (CDCl ₃ , ppm): -118.9 (s, 2F)

Synthesis Example 3 (Production of Polymer Compound A)

In a 200 mL flask in which the gas in the flask was replaced with argon gas, 500 mg (0.475 mmol) of the compound 9, 141 mg (0.427 mmol) of the compound 11 and 32 mL of toluene were added to make a homogeneous solution. The resulting toluene solution was bubbled with argon for 30 minutes. Then, 6.52 mg (0.007 mmol) of tris(diphenylmethyleneacetone)dipalladium and 13.0 mg of tris(2-methylphenyl)phosphine were added to the toluene solution, and the mixture was stirred at 100 ° C for 6 hours. Then, 500 mg of brominated benzene was added to the reaction liquid, and the mixture was stirred for 5 hours. Then, the flask was cooled to 25 ° C, and the reaction liquid was poured into 300 mL of methanol. The precipitated polymer was collected by filtration, and the obtained polymer was placed in a cylindrical filter paper, and extracted with methanol, acetone, and hexane for 5 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 100 mL of toluene, and 2 g of sodium diethyldithiocarbamate and 40 mL of water were added, and the mixture was stirred under reflux for 8 hours. After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, followed by washing twice with 3 mL of a 30 wt% aqueous acetic acid solution, followed by washing twice with 50 mL of water, followed by washing with 50 mL of a 5% potassium fluoride solution. After that, the mixture was washed twice with 50 mL of water, and the resulting solution was poured into methanol to precipitate a polymer. The polymer obtained by filtering and drying the polymer was redissolved in 50 mL of o-dichlorobenzene and passed through an alumina/ruthenium rubber column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 185 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound A.

The polymer compound A has the following repeating unit. Where n represents the number of repeating units.

Example 1 (Production of Organic Photoelectric Conversion Element)

The ITO patterned glass substrate having a film thickness of about 150 nm was formed by a sputtering method, washed with an organic solvent, an alkali detergent, and ultrapure water, and then dried. The glass substrate was subjected to ultraviolet ozone (UV-O ₃ ) treatment using an ultraviolet ozone (UV-O ₃ ) device.

A suspension of poly(3,4)ethylenedioxythiophene/polystyrenesulfonic acid dissolved in water (Bytron P TP AI 4083, manufactured by HC Stark Bytech Co., Ltd.) was filtered through a filter having a pore size of 0.5 μm. The filtered suspension was spin-coated on the ITO side of the substrate to a thickness of 70 nm. Next, after drying at 200 ° C for 10 minutes on a hot plate in the atmosphere, an organic layer was formed.

Next, o-dichlorobenzene and a fluorine-containing solvent hydrofluoroether (manufactured by Sumitomo 3M, <Novec>HFE7200) were mixed at a weight ratio of 99.4:0.6 to prepare a mixed solution. Next, a polymer compound A and [6,6]-phenyl C71-butyric acid methyl ester are added to the mixed solution to a weight ratio of 1: 2. Prepare a coating solvent. The amount of the polymer compound A added was 0.5% by weight based on the weight of the mixed solvent. The weight average component of the polymer compound A-converted polystyrene was 29,000, and the number average component of the converted polystyrene was 14,000. The wavelength of the light absorption end of the polymer compound A was 890 nm.

The stirrer was put into the coating solution, and stirred and mixed at a number of revolutions of 300 rpm to 1,000 rpm. Stirring mixing was carried out on a heated stirrer with variable temperature function at a set temperature of 70 °C. Then, the coating solution was filtered through a filter having a pore diameter of 0.5 μm, and the obtained filtrate was spin-coated on the organic layer, and dried in an atmosphere around nitrogen to form an active layer.

Titanium (IV) isopropoxide 97% (titanium (IV) isopropoxide 97%) purchased from SIGMA ALDRICH was mixed in isopropanol until its concentration became 1 wt., and the resulting liquid was spin-coated thereon. On the active layer, a film having a film thickness of 10 nm is formed, and then A1 is formed into a film of about 70 nm. The film thickness is the electrode formed. Next, an epoxy resin (rapid hardening type Araldite) is used as a sealing material, and the glass substrate is then subjected to a sealing treatment to obtain an organic thin film solar cell.

Comparative Example 1 (Production of Organic Photoelectric Conversion Element)

An organic photoelectric conversion element was produced in the same manner as in Example 1 except that o-dichlorobenzene was used in the coating solvent to replace the mixed solution of o-dichlorobenzene and hydrofluoroether.

(Evaluation of photoelectric conversion efficiency)

The shape of the organic thin film solar cell of the organic photoelectric conversion element obtained in Example 1 and Comparative Example 1 was a square of 2 mm × 2 mm. In these organic thin film solar cells, a certain amount of light is irradiated by using a Solar Simulator (manufactured by a spectrometer, trade name: CEP-2000 type, illuminance: 100 mW/cm ² ), and the generated current and voltage are measured. The photoelectric conversion efficiency can be calculated. The results are shown in Table 1.

[Possibility of application in industry]

According to the production method of the present invention, an organic photoelectric conversion element excellent in photoelectric conversion efficiency can be produced.

10‧‧‧Organic photoelectric conversion elements

20‧‧‧Substrate

32‧‧‧1st electrode

34‧‧‧2nd electrode

40‧‧‧Active layer

42‧‧‧1st active layer

44‧‧‧2nd active layer

52‧‧‧1st intermediate layer

54‧‧‧2nd intermediate layer

Fig. 1 shows an organic photoelectric conversion element in the production method of the present invention An example of the structure of the layer.

Fig. 2 is a view showing another example of the layer configuration of the organic photoelectric conversion element in the production method of the present invention.

Fig. 3 is a view showing another example of the layer configuration of the organic photoelectric conversion element in the production method of the present invention.

10‧‧‧Organic photoelectric conversion elements

20‧‧‧Substrate

32‧‧‧1st electrode

34‧‧‧2nd electrode

40‧‧‧Active layer

Claims (14)

A method for producing an organic photoelectric conversion element, which is a method for producing an organic photoelectric conversion element comprising an active layer containing a polymer compound between a pair of electrodes and a pair of electrodes, wherein the active layer comprises a polymer compound and a fluorine-containing solvent. Liquid formation. The method of claim 1, wherein the polymer compound is a polymer compound having a structural unit represented by the formula (1), [wherein, Ar ¹ and Ar ^{2 are the} same or different and represent a trivalent aromatic group; Z represents -O-, -S-, -C(=O)-, -CR ¹ R ² -, -S (= O)-, -SO ₂ -, -Si(R ³ )(R ⁴ )-, -N(R ⁵ )-, -B(R ⁶ )-, -P(R ⁷ )- or -P(=O (R ⁸ )-; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are the} same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkane. Thio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aralkylthio, decyl, decyloxy, decylamino, quinone imine, imine, amine Substituted amine, substituted indenyl, substituted indolyl, substituted indolyl, substituted indenyl, monovalent heterocyclic, heterocyclicoxy, heterocyclic thio, aralkenyl, aralkynyl, carboxy or Cyano; n represents 1 or 2; if n is 2, 2 Z may be the same or different]. The method of claim 2, wherein the polymer compound is a polymer compound further comprising any one of the structural formulas (2-1) to (2-10) below, [In the formulae (2-1) to (2-10), R ²¹ to R ⁴² each independently represent a hydrogen atom or a substituent; and X ²¹ to X ³⁰ each independently represent a sulfur atom, an oxygen atom or a selenium atom]. The method of claim 2, wherein the polymer compound is a polymer compound further comprising a structural unit represented by the formula (2), Wherein X ¹ and X ^{2 are the} same or different and represent a nitrogen atom or =CH-; Y ¹ represents a sulfur atom, an oxygen atom, a selenium atom, -N(R ⁴³ )- or -CR ⁴⁴ =CR ⁴⁵ -; R ⁴³ , R ⁴⁴ and R ^{45 are the} same or different and each represents a hydrogen atom or a substituent; W ¹ and W ^{2 are the} same or different and each represents a cyano group, a monovalent organic group having a fluorine atom, a halogen atom or a hydrogen atom]. The method of claim 4, wherein W ¹ is a fluorine atom. The method of claim 4, wherein W ¹ and W ² are fluorine atoms. The method of claim 4, wherein at least one of X ¹ and X ² is a nitrogen atom. The method of claim 4, wherein X ¹ and X ^{2 are} simultaneously a nitrogen atom. The method of claim 4, wherein Y ¹ is a sulfur atom or an oxygen atom. The method according to claim 1, which is a method for producing an organic photoelectric conversion element having a pair of electrodes and an active layer between a pair of electrodes, wherein the coating includes a polymer compound and a coating on one of the electrodes a step of forming a living layer by a liquid of a fluorine solvent, and a step of forming another electrode on the active layer. An organic photoelectric conversion element produced by the method described in claim 1 of the patent application. A liquid comprising a polymer compound having a structural unit represented by the formula (1) and a fluorine-containing solvent, [wherein, Ar ¹ and Ar ^{2 are the} same or different and represent a trivalent aromatic group; Z represents -O-, -S-, -C(=O)-, -CR ¹ R ² -, -S (= O)-, -SO ₂ -, -Si(R ³ )(R ⁴ )-, -N(R ⁵ )-, -B(R ⁶ )-, -P(R ⁷ )- or -P(=O (R ⁸ )-; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are the} same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkane. Thio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aralkylthio, decyl, decyloxy, decylamino, quinone imine, imine, amine Substituted amine, substituted indenyl, substituted indolyl, substituted indolyl, substituted indenyl, monovalent heterocyclic, heterocyclicoxy, heterocyclic thio, aralkenyl, aralkynyl, carboxy or Cyano; n represents 1 or 2; if n is 2, 2 Z may be the same or different]. The liquid according to claim 12, wherein the polymer compound contains, in addition to the structural unit represented by the formula (1), and includes any one of the formulae (2-1) to (2-10). Unit of polymer compound, The liquid solution according to the invention of claim 12, wherein the polymer compound contains a polymer compound having a structural unit represented by the formula (2) in addition to the structural unit represented by the formula (1). Wherein X ¹ and X ^{2 are the} same or different and represent a nitrogen atom or =CH-; Y ¹ represents a sulfur atom, an oxygen atom, a selenium atom, -N(R ⁴³ )- or -CR ⁴⁴ =CR ⁴⁵ -; R ⁴³ , R ⁴⁴ and R ^{45 are the} same or different and each represents a hydrogen atom or a substituent; W ¹ and W ^{2 are the} same or different and each represents a cyano group, a monovalent organic group having a fluorine atom, a halogen atom or a hydrogen atom].