TW201238994A - Method for producing photoelectric transducering element - Google Patents

Abstract

Provided is a method for producing a photoelectric transducering element having a pair of electrodes and an active layer between the pair of electrodes. The active layer contains a high molecular compound having a structure unit represented by formula (1) [wherein, Ar1 and Ar2 may same or diffenent, represent a three-valent aromatic group. Z represents -O-, -S-, -C(=O)-, -CR1R2-, -S(=O)-, -SO2-, -Si(R3)(R4)-, -N(R5)-, -B(R6)-, -P(R7)- or -P(=O)(R8)-. R1, R2, R3, R4, R5, R6, R7 and R8 may same or diffenent, represent hydrogen atom, halogen atom, alkyl group, alkoxyl group, thioalkyl group, aryl group, aryloxy group, arylthio group, arakyl group, arylakyloxy group, arylakylthio group, acyl group, acyloxy group, amide group, imide group, imino group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silyl amino group, mono-valent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, aryl alkynyl group, carboxyl group or cyano group. n represents 1 or 2. When n is 2, the two z's may same or different.]. According to the photoelectric transducering element producing method, the active layer is formed with a liquid containing a high molecular compound, a first solvent and a second solvent different from the first solvent, thus a photoelectric transducering element having excellent photoelectric transducering efficiency being obtained.

Description

201238994 6. DISCLOSURE OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method of manufacturing an organic photoelectric conversion element. [Prior Art] The organic photoelectric conversion element has the advantages of reducing the number of layers of the organic layer in the element, and manufacturing an organic layer by a printing method, and can be easily and inexpensively manufactured when compared with an inorganic photoelectric conversion element. However, the photoelectric conversion efficiency of the organic photoelectric conversion element is insufficient, which hinders its practical use. The organic photoelectric conversion element having an active layer formed using a solution containing a polymer compound P3HT and o-dichlorobenzene is not sufficient as described in Japanese Laid-Open Patent Publication No. 2009-158734. SUMMARY OF THE INVENTION The present invention is capable of producing a method for producing an organic photoelectric conversion element having high photoelectric conversion efficiency. ' Η 不 不 不 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机In the method for producing the conversion device, the active layer is formed of a solution containing a polymer compound and a second solvent different from the 21 solvent. —tr (1) where Ar1 and Ar2 may be the same or different, and Z represents +, -S~C(tetra)...CR; square fragrant: base. -Si(R3)(I〇-, _N(R5)—) is ~, )-, -Ρ(ί〇- or -P(=〇)(R8)—. 323941 201238994 • R1, R2, R3, R4 , R5, R6, R7 and V may be the same or different, and represent a hydrogen atom, a functional atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, a arylthio group, an aromatic alkyl group, and a aryl group. Oxygen, arylsulfanyl, aryl, aryloxy, w amide, oximine, imine, amine, substituted amine, substituted silyl, substituted fluorenyloxy , a substituted thiolthio group, a substituted fluorenylamino group, a monovalent heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an aryl group, a quaternyl group, an enantiomer group or a cyano group. η is 1 or 2 When η is 2, two Ζ may be the same or different. [Embodiment] The reduction size of each member in the drawings shown in the following description may be different from the actual one. Meanwhile, although the organic photoelectric conversion element is There is also a member such as a lead wire of the electrode, but it is not directly related to the description of the present invention. Therefore, it is omitted in the description and the illustration. In the following description, one of the thickness directions of the substrate may be referred to as "above". Or "upper", the other side of the thickness direction of the substrate is "lower" or "lower". This upper and lower relationship is set for the convenience of explanation, and is not necessarily applicable to the manufacturing steps of the actual manufacturing of the organic photoelectric conversion element and the use thereof. The basic configuration of the organic photoelectric conversion element to which the production method of the present invention is applied is a configuration having a pair of electrodes and an active layer. At least one of the pair of electrodes is transparent or translucent. One of the organic photoelectric conversion elements A transparent or translucent electrode among the electrodes, usually an anode. Meanwhile, an opaque or translucent electrode of a pair of electrodes, usually a cathode, is disposed at a pair of electrodes in the organic photoelectric conversion 7L. The active layer may be one layer or several layers. Meanwhile, a layer other than the active layer of 323941 5 201238994 may be disposed between a pair of electrodes, and this layer may also be referred to as an intermediate layer in this specification. It is a layer containing one or more types of organic compounds. At least one type of organic compound 'is a polymer compound containing a structural unit represented by formula (1). The compound may, for example, be an electron-donating compound (P-type semiconductor) or an electron-accepting compound (n-type semiconductor). The active layer may be a single layer or a laminate in which several layers are stacked. As for the form of the active layer, An active layer of a so-called ρη heterojunction type in which a layer (electron-donating layer) formed of an electron-donating compound and a layer (electron-accepting layer) formed of an electron-accepting compound are superposed; an electron-donating compound and an electron accepting The active compound in the present invention may be in any one of the forms in which the active compound is mixed to form a block heterojunction type active layer or the like of a bulk heterojunction structure. The activity in the organic photoelectric conversion element of the present invention The layer may be formed of a ruthenium molecule compound containing a structural unit represented by the formula (1), and a solution of a first solvent and a second solvent different from the first solvent. The active layer is preferably formed by applying a polymer compound containing a structural unit represented by the formula (1), a first solvent, and a second solvent different from the first solvent to the electrode on one side. An example of the layer constitution 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 case of the difference from the first drawing, and only the difference from the first drawing and the second drawing will be described. In the example of Fig. 1, the laminated body in which the active layer 40 is held between the first electrode 32 and the second electrode 34 is mounted on the substrate 20 to constitute an organic photoelectric element 323941 6 201238994. When light is collected from the substrate 20 side, the substrate 2 is transparent or translucent. At least either of the first electrode 32 and the second electrode 34 is transparent or transparent. When the light is collected from the substrate 20 side, the i-th electrode 32 is transparent or semi-transparent. One of the first electrode 32 and the second electrode 34 is an anode, and the other is a cathode, and is not particularly limited. For example, when the organic photoelectric conversion element 1 is fabricated by laminating the substrate 2 q side (four), when a film is used for film formation of a cathode (for example, aluminum or the like), the wire is placed in a later step. Therefore, in the case of this example, it is preferable that the i-th electrode 32 is an anode and the second electrode 34 is a cathode. At the same time, in this case, (4) it is highly probable that the thickness is not transparent or translucent. Therefore, in order to be able to illuminate the side of the substrate 2, 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 4 () is composed of two layers of the first active layer π and the second active layer 44, and is a pn heterojunction type active layer. The -layer among the t-active layer 42 and the second active layer 44 is an electron-accepting layer, and the other layer is an electron-donating layer. In the example of Fig. 3, the i-th intermediate layer 52 and the second intermediate layer 54 are provided. The first intermediate layer 52 is located on the active layer 40 and the first! Between the electrodes 32, 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 also be composed of several layers. The intermediate layer can have various functions. When the ith electrode 32 is set to the anode of 323941 7 201238994, 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. In this case, the second electrode 34 is a cathode. 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 electron-donating compound and the electron-accepting compound contained in the active layer are not particularly limited, and the relative energy level of the energy state of the compound can be determined. In the formula (1), the trivalent aromatic group represented by Ar1 and Ar2 may, for example, be a substituted aromatic hydrocarbon group or a substituted aromatic heterocyclic group. When the trivalent aromatic group represented by Ar1 and Ar2 is a substitutable aromatic hydrocarbon group, the structural unit represented by the formula (1) may, for example, have a structure of a condensed cyclic compound, a phenene, a carbazole or an anthracene. unit.

When the trivalent aromatic group represented by Ar1 and Ar2 is a substitutable arylene heterocyclic group, the structural unit represented by the formula (1) has, for example, the following structure. 323941 8 201238994 (2^4> ¢245) (246) (247) (248) /249)

(2S3) (294) <2S8>;9g9 ^Oga {2S6) (257) (258) (258) (262)

(2Φ)

(263)

(264) Examples of the electron-donating compound include a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, an oligomer 11 phenophene and a derivative thereof, and polyethylene. °ββ and its derivatives, poly-fever and its derivatives, polyoxyalkylene derivatives with aromatic amine residues in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives Polypyrrole and its derivatives, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, and polymer compounds containing structural units of the formula (1) 323941 9 201238994. 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) (Ρ3ΗΤ) is preferable. From the viewpoint of improving the photoelectric conversion efficiency, the polymer compound contained in the active layer is preferably represented by the formula (2-1) to (2-10) in addition to the structural unit represented by the formula (1). Structural unit. The structural unit in the present invention means a partial structure which can constitute a repeating unit or a repeating unit of a polymer compound.

(Μ)

In the formulae (2-1) to (2-10), R21 to R42 each independently represent a hydrogen atom or a substituent. Examples of the substituent represented by R21 to R42 include a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a sulfur-burning group which may have a substituent, an aryl group, an aryloxy group, and an aromatic sulfur. Base, arylalkyl, aralkyloxy, aralkylthio, aralkenyl, aralkynyl, amine, substituted amine, fluorenyl, substituted fluorenyl, fluorenyl, decyloxy, decylamino, hetero a cyclic group, a carboxyl group, a nitro group, and a cyano group which may have a substituent. R21, R22 and R35 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 an alkoxy group which may have a substituent The base is preferred, and the alkyl group which may have a substituent is more preferred. The viewpoint of improving the solubility of the polymer compound of the present invention 323941 10 201238994

In terms of R 21 and D22

R 35 and R are branched garden bases R23, R24, 俨, r'r31, r32, R33, r3 3 4 . R.ff (iv) atom and hydrogen atom, fine fluorine atom and hydrogen atom preferably = more preferably hydrogen atom R25, R26 instead of red / RiR3 ° a4 atom, (iv) atom, may have m base and branch, and money atom and The green base is preferred. R is preferably a (10) sub, a (iv) atom, a county, and a methoxy group, and a decyloxy group. And in the formula (2-1) to (2-1〇), X21 $ γ3. The β sub, ... 乂 are independent of each other representing a sulfur atom or a litho atom. In order to increase the short-circuit current interconnection density of the photoelectric conversion element having the organic layer containing the polymer compound of the present invention (short-circuit current is difficult, it is preferably a sulfur atom and an oxygen atom, and a neosulfide material is preferred. In terms of the short-circuit current interconnection density of the photoelectric conversion element of the organic layer of the polymer compound of the invention, the polymer compound preferably has the formula (5)), the formula (2-2), the formula (2-3) or the formula (2-10). The structural unit of the formula (4), and having a structural unit represented by the formula (2-1), the formula (2-2) or the formula (2-10), preferably having the formula (2-1) or the formula (2-1)结构) indicates that the structural unit is better, and the structural unit represented by the formula (2-10) is particularly preferable. In addition to the structural unit represented by the formula (1), it is preferable to further contain a polymer compound having a structural unit represented by the formula (2).

W2 (2) 323941 11 201238994 wherein 'X1 and χ2 may be phase π indicating a sulfur atom, an oxygen species or a different, indicating a nitrogen atom or R43, R44 and a selenium atom, -N(R43)_ or -CR44,45-. W2 may be the same or not; and the object::: two' represents a hydrogen atom or a substituent. Wl and dentate atoms or hydrogen atoms. The fluorinated group and the monovalent organic group of the fluorine atom are all nitrogen atoms and are not gas atoms or = CH-. And in the two formulas (2) of X1 and X2, Wl W2 may be a valence of a monovalent gas or a hydrogen atom having a cyano group or a fluorine atom. The fluorine atom is a lightening group: a gasified acetylation group, a sulphur group, and a fluoro group, and examples thereof include a fluorinated group. As a 4-primary atom, a gas atom, a desert atom, and an iodine atom. In the case where the formula (2) indicates the absorption strength of the polymer compound of the structural unit, w1 and W2 are preferably oxygen atoms. In the formula (2), Y represents a sulfur atom, an oxygen atom, a selenium atom, -N(R46)- or -CR~CRR'. R47 and R48 may be the same or different and each represents a hydrogen atom, a dentate atom or a substituent. 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 arylsulfanyl group, a decyl group, a decyloxy group, and the like. Amidino, oximine, imine, amine, substituted amine, substituted fluorenyl, substituted fluorenyloxy, substituted fluorenylthio, substituted fluorenylamino, monovalent heterocyclic, hetero Epoxy, heterocyclic thio, aralkenyl, aralkynyl, carboxy, cyano. 323941 12 201238994 . From the viewpoint of the absorption strength and solubility of the polymer compound containing the structural unit represented by the formula (1), γ is preferably a sulfur atom or an oxygen atom. The halogen atom in the present invention is a fluorine atom, a chlorine atom, a bromine atom and a W 峨 atom. The alkyl group ' in the present invention may be linear or branched, or may be in the form of a ruthenium. The carbon number of the alkyl group is usually from 丨 to 3〇. Specific examples of the alkyl group include a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a first butyl group, a second butyl group, a n-pentyl group, and an isopentyl group. Nonylbutyl, i-mentyl butyl, n-hexyl, isohexyl, 3-methylpentyl, 2-decylpentyl, methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl , 3,7-didecyloctyl, fluorenyl, fluorenyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octayl, etc., chain alkyl, cyclopentyl, a cycloalkyl group such as a cyclohexyl group or an adamantyl group. The alkoxy group in the present invention may be linear or branched, or may be cyclic. The carbon number of the alkoxy group is usually from 丨 to 20. Specific examples of the alkoxy group include a decyloxy 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-monomethyloctyloxy, 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 fluorenyloxymethyl group. A fluorinated alkoxy group having 1 to 20 carbon atoms such as 2-methoxyethoxy. The alkylthio group in the present invention may be linear or branched, or may be a cycloalkylthio group. The carbon number of the alkylthio group is usually from 1 to 2 Torr. Specific examples of the sulfur-burning group 323941 13 201238994 include mercaptothio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, and tert-butyl group. Thio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ylhexylthio group, mercaptothio group, mercaptothio group, 3, dimercaptooctyl Alkylthio, dodecylthio, trifluoromethylthio. The aryl group in the present invention has a carbon number of usually 6 to 6 Å. Specific examples of the aryl aryl group include a phenyl group and a C1 to C12 alkyloxyphenyl group (the ci to C12 alkyl group is an alkyl group having 1 to 12 carbon atoms. The ci to C 2 alkyl group is preferably C1 to C8. An alkyl group, preferably a C1 to C6 alkyl group, a C1 to C8 alkyl group, an alkyl group having 1 to 8 carbon atoms, and a ci to C6 alkyl group, representing a carbon number i to 6 as a C1 to C12 alkyl group. Specific examples of the C1 to C8 alkyl group and the C1 to C6 alkyl group include the groups illustrated in the above alkyl group. The same applies to the following. /, 'ci to C12 alkyl group, 1-naphthyl group, 2- The naphthyloxy group in the present invention has a carbon number of usually 6 to 60. Specific examples of the aryloxy group include a silyloxy group and a C1 to C12 alkyloxy group stupid oxyfluoride. , C1 to C12 alkyloxy, 1-naphthyloxy, 2-naphthyloxy, pentafluorooxyl. The arylthio group in the present invention has a carbon number of usually 6 to 60. As an arylthio group Specific examples thereof include a phenylthio group, a C1 to C12 alkylsulfonylthio group, a C1 to C12 alkyl stearyl group, a fluorenyl-naphthylthio group, and a 2-naphthylthio group as a substituted arylthio group. The pentafluorophenylthio group. The aralkyl group in the present invention has a carbon number of usually 7 to 6 Å. Specific examples of the alkyl group include a phenyl-C1 to C12 alkyl group, a C1 to C12 alkyl alkoxyphenyl-C1 to C12 alkyl group, a C1 to C12 alkylphenyl-ci to a C12 alkyl group, and a naphthyl group. C1 to C12 alkyl, 2-naphthyl-C1 to C12 alkyl. 323941 201238994 The arylalkoxy group in the invention has a carbon number of usually 7 to 60. Specific examples of the aryl alkoxy group can be mentioned. a phenyl-α to C12 alkyloxy group, a C1 to C12 alkyloxyphenyl-ci to ci2 alkyloxy group, a C1 to C12 alkylphenyl-C1 to C12 alkyloxy group, a naphthyl group-C1 to C12 alkyloxy, 2-naphthyl-C1 to C12 alkyloxy. The arylalkylthio group in the invention has a carbon number of usually 7 to 6 Å. As a specific example of an aryl thiol group, Illustrative of _C1 to Ci2 alkylthio, C1 to C12 alkyloxyphenyl-C1 to C12 alkylthio, ci to C12 alkylphenyl-C1 to C12 alkylthio, naphthyl_C1 To a C12 alkylthio group, a 2-naphthyl-C1 to C12 alkylthio group. The fluorenyl group in the present invention has a carbon number of usually 2 to 2 Å. Specific examples of the fluorenyl group include an ethyl fluorenyl group. , propyl sulfhydryl, butyl sulfhydryl, isobutyl decyl, trimethyl ethenyl, benzhydryl, trifluoroethyl The fluorenyloxy group in the present invention has a carbon number of usually 2 to 20. Specific examples of the decyloxy group include an ethyl oxy group, a propyl oxy group, and a butyl oxy group. Alkyl, isobutyloxy, tridecylethoxycarbonyl, alkoxy, trifluoroacetoxy, pentafluorobenzoquinone. The carbon number of the amine group is usually from 1 to 20. The guanamine group is a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an acid amide. Specific examples of the guanamine group include a decylamino group, an acetamino group, a propylamine group, Butylated amino group, benzoguanamine group, trifluoroacetamido group, pentafluorophenylamino group, diammonium group, diethylamino group, dipropylammonium group, dibutylammonium group, Dibenzimidyl, di-trifluoroacetamido, bis-pentafluorobenzoguanamine. The quinone imine group ' in the present invention means a group obtained by removing a hydrogen atom bonded to a nitrogen atom of 323941 15 201238994 from a hydrazine 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 has a carbon number of usually 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, and Diisopropylamino, butylamino, isobutylamino, tert-butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2 -ethylhexylamino, decylamino, decylamino, 3,7-didecyloctylamino, dodecylamino, cyclopentylamino, dicyclopentylamino, cyclohexyl Amino, dicyclohexylamine, 吼π each, butyl, bistrifluorodecylamino, phenylamino, diphenylamino, C1 to C12 alkyloxy styryl , a (C1 to C12 alkyloxyphenyl)amino group, a di(C1 to C12 alkylphenyl)amino group, a 1-naphthylamino group, a 2-naphthylamino group, a pentafluorophenylamino group,比β-pyridylamino, hydrazine-based, pyrimidinylamino, morphinylamino, tridecylamino, phenyl-C1 to C12 alkylamino, C1 to C12 alkyloxyphenyl -C1 to C12 alkylamino group, C1 to C12 alkylphenyl-C1 to C12 alkylamino group, di(C1 to C12 alkyl group) Alkylphenyl-C1 to C12 alkyl)amino group, di(C1 to C12 alkylphenyl-C1 to C12 alkyl)amino group, naphthyl-C1 to C12 alkylamino group, 2-naphthyl-C1 to C12 Alkylamino group. The substituted alkylene group in the invention may, for example, be a trimethylsulfanyl group, a triethylsulfonyl group, a tri-n-propylsulfonyl group, a triisopropylsulfonyl group, a tert-butyl fluorenyl group, a triphenyl group. Basestone, tris-p-xylphenyl fluorenyl, tritylmethyl fluorenyl, diphenyl fluorenyl fluorenyl, tert-butyldiphenyl fluorenyl, diterpene basic group. 323941 16 201238994 • ^ As the substituted mercaptooxy group in the present invention, for example, trimethylsulfonyl**, triethylmethyloxyl, tri-n-propylpropyloxy, triisopropyltin "Lactyl-based, tert-butyl decyl decyloxy, tris-n-decyloxy, tri-indolyl-yloxy, di-indolyl-indenyloxy, diphenylindolyl a mercaptooxy group, a butyl butyl diphenyl fluorenyloxy group, a dimethyl phenyl thiol group. The substituted fluorenylthio group in the invention may, for example, be a trimethylsulfonylthio group or a trisyl group. Ethyl thiolthio, tri-n-propyl sulphate, trisylthio, tert-butyldimethyl sulphoyl, trisyl thiol, trimethyl phenyl A thiolthio group, a tritylmethylthio group, a diphenylmethyl fluorenylthio group, a third τyldiphenyl 7 thio group, a dimethyl benzyl (tetra)thio group. The substituted silk amine group in the present invention may, for example, be trimethyl sulphate=, triethyl sulphate, tri-n-propyl sulphonylamino, triisopropyl sulphate-based, second τ-based Dimercapto-ylamino, triphenyl 11-amino, trimethyl-tolylhydrazino, tritylmethylamino, diphenylmethyl fluorene 2-amine, second Diphenyl 7-amino group, dimethylphenyl coughylamino, mono(dimethylmethyl)amino, bis(triethyldecyl)amine, bis(tri-n-propyl)amine Base, mono(diisopropyldecyl)amine, bis(t-butyldimethyl Z-ylamino, bis(triphenylphosphino)amino, bis(tri-p-dimethylphenyl) Amino, bis(diphenylf-decyl)amino, bis(diphenylfluorenylfluorenyl)amine 2-(t-butyldiphenylfluorenyl)amine, bis(dimethylphenylhydrazine) The base 1 is a monovalent heterocyclic group in the present invention, and examples thereof include furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, sirolidazole, and imidazole. (imidazolidine), π-pyrazole, pyridinium 323941 17 201238994 〇 0 0 (pyrazolidine), 0 咱 咱 (furazan), 三零坐, 嚷二唆, oxadiazole, Sijun, "»比喃,. Bixian, pie bite, sulfur η 喃, tower 哄, β 密, pyridine, piper, morpholine, three tillage, benzofuran, isobenzofuran, benzophenone, oxime, oxime, indolizine, diargon σ 丨 朵 朵 (indoline), iso-dihydroanthracene, chromene, chromane, chromocene, benzopyrene, benzopyrene, 喧, 啥, 哄, benzophenone Benzene 11 stopper 11 sitting, sputum, naphthalene bite (11 & mouth 111:1^14 (1丨116), 〇|: 喔淋, 喧嗤琳, quinazolidine, cinnoline , phthalazine, cockroach, butterfly beta, 0 card saliva, sputum, phenanthrene bite, bite, point--------------------------------------------------------------------- a group in which a hydrogen atom is removed from a heterocyclic compound such as phenoxathiin, phenazine, phenazine, or phenazine. The monovalent heterocyclic group is preferably monovalent. Aromatic heterocyclic group. As in the present invention Examples of the heterocyclic oxy group include a group represented by the formula (4) in which an oxygen atom is bonded to the monovalent heterocyclic group. Examples of the heterocyclic thio group include a formula in which a sulfur atom is bonded to the monovalent heterocyclic group (5). ) the basis of the statement.

Ar7—〇- Ar7—S— (4) (5) In the formulae (4) and (5), Ar7 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 thiophenoxy group, a C1 to C12 alkylthiophenoxy group, a pyrroxy group, a furyloxy group, a pyridyloxy group, a C1 to C12 alkylpyridyloxy group, and an imidazolium group. Base, % oxazolyloxy, triazolyloxy, oxazoloxy, thiazolyloxy, thiadiazolyloxy. 323941 18 201238994 The heterocyclic thio group in the present invention has a carbon number of usually 2 to 60. Specific examples of the heterocyclic thio group include a thiophenethiol group, a C1 to C12 alkylthiophenethiol group, a pyrrolethiol group, a furanthiol group, a pyridinethiol group, and a C1 to C12 w alkyl group. Than a bit of a thiol group, a stilbene thiol group, a σ ratio of a thiol group, and a third. Sitting on a thiol group, a carbazole thiol group, a thiazole thiol group, a thiadiazole thiol group. The aralkenyl group in the invention usually has a carbon number of 8 to 20, and a specific example of the arylalkyl group is a styryl group. The aralkynyl group in the present invention usually has a carbon number of 8 to 20. Specific examples of the arylalkynyl 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). (2) In the formula, Ar3 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 second group. Examples of the heteroaryl group include a π-propanyl group, a specific ratio of a ratio of two groups, and a ratio of a ratio of two groups. 323941 19 201238994 A preferred form of the structural unit represented by the formula (1) is a group represented by the formula (3). In the formula (3), Ar11 and Ar12 may be the same or different and each represents a trivalent heterocyclic group. X3 means -〇-, -s-c(=〇), -s〇〇)-, -s(=o)~, _s〇2_, -Si(R9)(R4)-, -N(R5) _, -B(R6)-, -P(R7)- or -P〇〇)(r8)_. R4, R5, R6, R7, R8 and R9 may be the same or different and represent a gas atom, a halogen atom, a decyl group, a methoxy group, a thiol group, an aryl group, an aryloxy group, an arylthio group, a aryl group, Aromatic oxy, arylsulfanyl, aryl, St oxy, decyl, fluorenylene, imine, amine, substituted amine, substituted; 5 oxime, substituted fluorenyloxy, substituted A mercaptothio group, a substituted mercaptoamine group, a monovalent heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an aralkenyl group, an aralkynyl group, a carboxyl group or a gas group. RS0 and R51 may be the same or different and represent a hydrogen atom, a halogen atom, a radical, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkyloxy group, or an aromatic sulfur-burning sulfur. Base, fluorenyl, decyloxy, decylamino, quinone imine, imine, amine, substituted amine, substituted aryl, substituted aryl, substituted thiolthio, substituted fluorenyl a monovalent heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an aryl group, an aryl alkynyl group, a aryl group or a cyano group. X 3 and Ar 21 are adjacent to each other in the hetero ring contained in Ar 11 , C ( R5°) (r51) and Ar11 are adjacent sites of the heterocyclic ring contained in Ar21. In the formula (3), Ar11 and Ar21 may be the same or different and each represents a trivalent heterocyclic group. The trivalent heterocyclic group refers to an atomic group remaining after the removal of three hydrogen atoms from the heterocyclic compound 323941 20 201238994. The heterocyclic compound herein means an organic compound having a cyclic 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. (201) (hence <203) ¢04) (203⁄4 (206) (207) (208) (209) (210)

(211) (212) (213) (214) (215)

(216) (217) (218) (219) 323941 21 201238994 (220) (221) (222) (223) (224) (Zt5) (228) (227) (228) -〇p (228) (230 )

(232) (233) (234) (23S) (230) (237) 323941

(238) (23Θ) (240) (241) (242)

(243} 22 201238994 (244) (246) (248)

(247) (24β) {249)

"0c0 Λ R· R, (2M) (251) (252)

i* ¢53) (254) (255) )〇^cr (256) (257) (258) χςχτ :o^a (259) (2Θ0) (2Θ1) bits®2) (26?) (2Θ4) 323941 23 201238994 Λί (268) (2®)

(272) (273) (274) :〇^·瓜于从 (275) (276) (277} (27Θ) Politics 2 (27Θ) (280) (281) (282)

(283)

(284) In the formulae (201) to (284), R' may be the same or different and represent a hydrogen atom, a functional atom, a pyridyl group, an alkoxy group, a thiol group, an aryl group, an aryloxy group, or an aromatic sulfur. Alkyl, aralkyl, aralkoxy, aralkylthio, substituted amine, decyloxy, decylamino, aralkenyl, aralkynyl, monovalent heterocyclic or cyano. R" may be the same or different and represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a substituted fluorenyl group, a fluorenyl group or a monovalent heterocyclic group. In the formula (3), at least one of Ar11 and Ar21 is preferably self. The thiophene ring is preferably a group after removing three hydrogen atoms, and is preferably a group after removing three hydrogen atoms from the hexaphene ring. In the formula (201) to the formula (284), the trivalent heterocyclic group is preferably The heterocyclic group having a sulfur atom of 323941 24 201238994 is preferably a group represented by the formula (268) or the formula (273), and more preferably a group represented by the formula (273). R5° and R51 are preferably the same. Or a different 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, an aryloxy group having 6 or more carbon atoms, and a carbon number of 6 The above arylthio group, 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, a fluorenyl group having 6 or more carbon atoms, and a fluorene having 6 or more carbon atoms The group is preferably 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, and more preferably having a carbon number of 6 or more. Good. As with (1) The polymer compound of the structural unit shown can be exemplified as the polymer compound A. The polymer compound A having the following repeating units. In the formula, [eta] is a number of repeating units.

The polymer compound having 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. 323941 25 201238994 As the electron-donating compound, in addition to the polymer compound having the structural unit represented by the formula (1), for example, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, and a triphenyl group may be mentioned. a bis-diamine derivative, an oligothiophene and a derivative thereof, a polyvinyl carbazole and a derivative thereof, a polydecane and a derivative thereof, a polyoxyalkylene derivative having an aromatic amine residue in a side chain or a main chain, Polyaniline and its derivatives, poly 11 phenophene and its derivatives, poly 11 to p and its derivatives, polyphenylene vinyl and its derivatives, polythiophene ethylene and its derivatives. The electron-donating compound may be used alone in the active layer, or two or more kinds may be used in combination in the active layer. Examples of the electron accepting compound include oxadiazole derivatives, decanedioxane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, hydrazine and its derivatives, and tetracyanoquinone. Terpene methane and its derivatives, ketone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-meridene and its derivatives, Polypyridin and its derivatives, polypyridamole and its derivatives, polyfluorene and its derivatives, fullerene and its derivatives such as C6〇, phenanthrene derivatives such as bathocuproine, titanium oxide, etc. Metal oxides, carbon nanotubes, etc. As the electron accepting compound, titanium oxide, a carbon nanotube, a fullerene, and a fullerene derivative are preferable, and a fullerene and a fullerene derivative are particularly preferable. A fullerene derivative is a compound which represents at least a portion of a fullerene which has been modified. Examples of the fullerene include C6G fullerene, C7G fullerene, C76 fullerene, C?8 fullerene, and C84 fullerene. 323941 26 201238994 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).

Rb Rb I I

In the formulae (6) to (9), Ra is an alkyl group, an aryl group, a heteroaryl group or a group having an ester structure. Several Ras can be the same or different. Rb represents an alkyl group or an aryl group. Several Rbs can be the same or different.

The group having an ester structure represented by Ra may, for example, be a group represented by the formula (10). —Rc 〇(10) (wherein ul is an integer representing 1 to 6, u2 is an integer representing 0 to 6, and Re is an alkyl group, an aryl group or a heteroaryl group.) As a heteroaryl group in the present invention Specific examples thereof include a thienyl group, a pyridyl group, a fluorenyl group, a π-bite group, a fluorene group, and an isoindole group. Examples of the fullerene and fullerene derivatives include C6D, C70, C76, C78, C84 and derivatives thereof. The following compounds are exemplified as the CeO fullerene derivative and the C7D fullerene derivative. 323941 27 201238994

Meanwhile, as an example of the fullerene derivative, [5, 6]-phenyl C61 butyric acid ([5, 6]-PCBM), [6, 6]-phenyl C6i butyric acid A CeoPCBM' [6, 6]-phenyl Cei butyric acid methyl ester), [6, 6]-phenyl C71 butyric acid methyl ester (C7〇PCBM '[6, 6]-phenyl C71 butyric acid methyl ester), [6, 6 phenyl Css, C6PCBM, [6,6]-phenyl Css butyric acid methyl ester), [6,6]-nonyl Cei butyrate ([6, 6] -thienyl Cei butyric acid methyl ester). When the active layer contains an electron-donating compound and a fullerene derivative, it is inclined to 100 parts by weight of the electron-donating compound, and the ratio of the fullerene derivative in the active layer is preferably 10 to 1,000 parts by weight. 20 to 500 323941 28 201238994 Weight parts are preferred. The electron-accepting compound may be used in the active layer as a compound, or a combination of two or more compounds may be used in the active layer. The active layer in the organic photoelectric conversion device of the present invention may be formed of a solution containing a polymer compound containing a structural unit represented by the formula (1) and a second solvent of the i-th solvent and the first solvent. Examples of the first solvent and the second solvent include water and an organic solvent. When the first solvent is an organic solvent, examples of the organic solvent include toluene, xylene, mesitylene, tetrahydronaphthalene, decahydrocaine, bicyclohexyl, n-butylbenzene, and t-butyl. Unsaturated smoke solvents such as benzene and tert-butylbenzene, four gasified carbon, gas imitation, dichlorocarbyl, Erqiyiyuan, Qidingyuan, bromobutane, pentane, bromopentane, and hexane , bromine, cyclohexane, bromocyclohexane, etc., a saturated hydrocarbon solvent (especially a gasified saturated hydrocarbon solvent), a halogenated unsaturated hydrocarbon solvent such as benzene, diphenylbenzene or trigasbenzene (especially gas) An unsaturated hydrocarbon solvent), an ether solvent such as tetrahydrofuran, tetrahydropyran or diphenyl ether. The solubility of the polymer compound containing the structural unit represented by the formula (1) is S. The first solvent is preferably a halogenated unsaturated hydrocarbon solvent, and the aromatic gas compound is preferred, and the second gas benzene is more preferred. Dioxin is especially good. The second solvent is a solvent different from the first solvent, and examples thereof include toluene, mono-toluene, mesitylene, tetrahydronaphthalene, decahydronaphthalene, dicyclohexane, n-butylbenzene, and dibutylbenzene. Unsaturated hydrocarbon solvent such as tributylbenzene, tetra-carbonized carbon, gas-like, dichlorohydrazine, di-hexane, gas-fired, brominated butadiene, pentane, bromopentane, hexane, bromo Halogenated saturated hydrocarbon solvents such as alkane, cyclohexane, bromocyclohexane, etc. (especially gasified saturated hydrocarbon solvents), halogenated unsaturated hydrocarbon solvents such as benzene, dichlorobenzene, and trigas 323941 29 201238994 benzene (especially gasification) Unsaturated smoke solvent), an ether solvent such as tetrahydrofuran, tetrahydropyran or diphenyl ether. The second solvent is preferably an aliphatic gas compound, tetrahydronaphthalene or diphenyl mystery, and is preferably an aliphatic gas compound, preferably a gas imitation or a dioxane, and particularly preferably chloroform. The solubility of the polymer compound containing the structural unit represented by the formula (1) is preferably such that the second solvent is mixed in the range of 0.001% by weight to 99.999% by weight based on the weight of the first solvent. It is preferred to mix in the range of from 1% by weight to 99.9% by weight. One of the first solvent and the second solvent may be a solvent having a low solubility of the polymer compound containing the structural unit represented by the formula (1). The solvent having a low solubility of the polymer compound containing the structural unit represented by the formula (1) is N-mercapto-2-tetrahydroindole pirone (!^-11161:1^1-2) -0丫1*1*〇11(1〇11)(23.1(]/〇113)1/2), dimethyl sulfoxide (24. 5(J/cm3) 1/2) 2-propanol (23.5 (J/cm3) 1/2), methanol (29.7 (J/cm3) 1/2), etc. The value in () indicates the solubility. The SP value of the parameter. Here, the SP value (solubility parameter (5)) is a value defined by the regular solution theory introduced by H i 1 debrand, and it is known that the solubility of the two-component solution can be approximated. In the regular solution theory, since the interaction between the solvent and the solute is only intermolecular force, the dissolution parameter can be used as a scale indicating the intermolecular force. Although the actual solution is not limited to the regular solution, it is still empirically It is understood that the smaller the difference between the SP values of the two components, the larger the solubility. The amount of the 301941 30 201238994 added to the solvent of the structural unit represented by the formula (1) is not particularly limited, but may be suitable. The optimum range is 〇丄**% by mass or more, and preferably 0.3% by weight or more, based on the total amount of the first solvent and the weight of the second solvent, and is 5% by weight. Preferably, the polymer compound containing the repeating unit represented by the formula (1) and the liquid (the solvent and the second solvent different from the first solvent) contain an electron accepting compound and a polymer compound containing a repeating unit represented by the formula (1). In the case of the electron-donating compound, the total amount of the electron-donating compound in the liquid and the amount of the electron-donating compound are usually 〇·2% by weight or more and 2% by weight or less', and preferably 0.5% by weight or more and 10%. The weight ratio is preferably 1% by weight or more and 5 parts by weight. The compounding ratio of the electron-donating compound to the electron-accepting compound is usually from : to :' and preferably from 1 to 10: 10 to 1' Preferably, the content of the electron-donating compound and the electron-accepting compound in the solution is usually 0.4 in the case of separately preparing a solution of the electron-donating compound solution and the electron-accepting compound. The amount of % or more is preferably 6% by weight or more, and preferably 2% by weight or more. The organic photoelectric conversion device of the present invention is usually produced by coating a side electrode with a south molecular compound, an ith solvent, and After the active layer is formed in the solution of the second solvent having the different i-th solvent, the other electrode may be formed on the active layer. When applying, it is preferable to use a spin coating method, a casting pressure*, a micro-concave coating method, or a concave plate coating. Method, strip coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, gravure printing method, bending printing method, offset printing 323941 31 201238994 brush method, inkjet printing method , disperser printing method, nozzle coating method, capillary coating method, and the like. Among them, the spin coating method, the bending printing method, the gravure printing method, the ink jet printing method, and the disperser printing method are preferable, and the spin coating method is preferable. 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 of two or more different frequencies, and then treated. The solution is coated on the electrode or the intermediate layer to evaporate the solvent to form an active layer. On the other hand, when the active layer is a pn heterojunction type organic photoelectric conversion element, for example, a solution containing an electron-donating compound and a solution containing an electron-accepting compound can be applied 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 of the electron-accepting compound after the same treatment is applied onto the electron-donating layer to evaporate 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 be reversed from the above. The thickness of the active layer is usually from 1 nm to 100 μm, and is preferably from 2 nm to 1,100 nm, and is preferably from 5 nm to 500 nm, more preferably from 20 nm to 200 nm. The substrate may be any substrate that does not chemically change when the organic layer is formed after the electrode is formed. Examples of the material of the substrate include glass, plastic, polymer film, and enamel. In the case of an opaque substrate, it is preferred that the other electrode 323941 32 201238994 (ie, the electrode of the pair of electrodes that is further 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, it is preferably a film made of a conductive material such as indium oxide, oxidized, tin oxide, or the like, such as indium tin oxide (ΙΤ0), indium zinc oxide (ΙΖ0), or NESA, or gold, platinum, or silver. A metal thin film such as copper is preferably a film made of a conductive material formed of ΙΤ0, indium zinc oxide, tin oxide or the like. As a method of producing the electrode, for example, a vacuum deposition method, a sputtering method, an ion plating method, a plating method, or the like can be exemplified. 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 may be non-transparent 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 chain, sodium, potassium, rubidium, cesium, magnesium, about, lanthanum, lanthanum, aluminum, lanthanum, hunger, zinc, lanthanum, indium, lanthanum, cerium, lanthanum, money, lanthanum. Or a metal; two or more alloys of the above metals; one or more of the foregoing metals and one selected from the group consisting of gold, silver, platinum, copper, lanthanum, titanium, auric, 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 town-indium alloy, a town--g alloy, an indium-silver alloy, a Li-Ming alloy, a Li-Qin alloy, a per-indium alloy, and a bow-and-make alloy. The material of the intermediate layer may, for example, be a metal halide such as a fluoride (L i F) or a halide or oxide of an alkaline earth metal, or an inorganic semiconductor microparticle such as titanium oxide or a metal alkoxide. £001' (poly(3,4)ethylenedioxythiophene). Among the materials such as 323941 33 201238994, the intermediate layer on the anode side is preferably a layer formed of PED0T. The intermediate layer on the cathode side is preferably a layer formed of a metal halide (preferably in LiF), a thin film of titanium oxide formed by isopropanol, and a layer formed of lithium fluoride (LiF), formed of titanium isopropoxide. The titanium oxide thin film layer is preferred. The organic photoelectric conversion element produced by the production method of the present invention can emit a photoelectromotive force between electrodes by irradiating a transparent or translucent electrode such as sunlight, thereby functioning as an organic thin film solar cell. It is also possible to collect a plurality of organic thin film solar cells and use them as an organic thin film solar cell module. When a voltage is applied between the electrodes or in an unapplied state, the photocurrent can be caused by irradiating the light to the transparent or translucent electrode, thereby functioning as an organic photosensor. Several organic light sensors can also be used together as an organic image sensor. The organic thin film solar cell' is basically the same modular 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 cover glass is filled 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 forming a cell thereon, a structure for taking light from the side of the transparent supporting substrate is formed. Specifically, a module structure called a SUPER straight type, a substraight type, a p〇tting type, and an integrated substrate used in an amorphous germanium solar cell are known. Molded structure, etc. The organic thin film solar cell of the present invention can also be suitably selected according to the purpose of use or the place of use and environment. 323941 34 201238994 A representative ultra-straight or sub-straight module is a battery that is disposed at a certain interval between the support substrates that are transparent on one side or both sides and that are subjected to anti-reflection treatment. The current is connected to the outer edge portion by a metal wire or a flexible wire or the like to form a structure in which the generated electric power can be taken out. Between the substrate and the battery, a film or a variety of plastic materials such as ethylene vinyl acetate (EVA) in a resin form may be used for the purpose of improving the protection or power collection efficiency of the battery. At the same time, if the impact from the outside is small and the surface is not required to be coated with a hard material, the surface protective layer may be formed by a transparent plastic film, or the filling resin may be hardened to provide a protective function, and the support substrate may not be supported on one side. 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. As long as the battery body or the support substrate, the filling material, and the sealing material are made of a flexible material, a solar cell can be formed on the curved surface. When a solar cell of a flexible branch body such as a polymer film is used, a battery is sequentially formed while the curled support is fed out, and the battery is cut to a desired size, and then the peripheral portion is bendable and resistant. The wet material is post-sealed to make the battery body. Can also be made into Solar Energy

The module structure called "SCAF" described in Materials and Solar Cells, 48, p383-391 "and the solar cell using the flexible support" can also be used in the case of curved glass or the like. When an insoluble component or dust is present in the solution during film formation, cracking occurs on the coating film, and 'non-essential components or dust nucleate to produce agglomerates. Therefore, the electrical and chemical contact of the joint interface is poor, or the electricity is generated by 323941 35 201238994. After reducing these conditions, the photoelectric conversion efficiency can be improved. [Examples] Synthesis Example 1 (Synthesis of Compound 1)

The gas in the flask was replaced with argon gas in a four-necked flask of 〇〇〇mL, and 3-bromothiophene 13.0 g (80. Ommol) and diethyl ether (80 mL) were added to make a homogeneous solution. The solution was maintained at -78 T:, and 2. 6 M of a hexane solution of n-butyllithium (n-BuLi) (31 mL (80·6 mmol)) was added dropwise. After reacting at -78 ° C for 2 hours, the 3-thiophene was dissolved in 2 mL of diethyl ether.

8. 96 g (80. Ommol) solution. After the dropping, the mixture was stirred at -78 ° C for 30 minutes and then at room temperature (25 ° C) for 30 minutes. The reaction solution was re-cooled to -78 ° C, and a hexanes solution of 2.6 M of n-Bu. 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 solution was cooled to _25 ° C, and a solution of 6 〇g (236 mmol) of iodine dissolved in 1, diethyl ether was dropped over 30 minutes. After the dropwise addition, 50 mL of a 1 N aqueous sodium thiosulfate solution was added thereto at room temperature (25 ° 〇 stirring for 2 hours) to stop the reaction. After the reaction product was extracted with a binary puzzle, the reaction product was dried over magnesium sulfate, and after filtration, The filtrate was concentrated to obtain 35 g of a crude product. The crude product was recrystallized and purified using chloroform to obtain 28 g of Compound 1. (Synthesis of Compound 2) 323941 36 201238994

In a 300 mL four-necked flask, 1 g. 5 g (23.4 mmol) of bisiodothiophene methanol (Compound 1) and 150 mL of dichloromethane were added to make a homogeneous solution. After 7.50 g (34.8 mmol) of pyrochromic acid pyridinium salt was added to the solution, the mixture was stirred at room temperature (25 ° C) for 10 hours. After the reaction mixture was filtered to remove the insoluble material, the filtrate was concentrated to give 10.0 g (22.4 mmol) of Compound 2. (Synthesis of Compound 3)

0克(24.5 mmol), 2, copper powder 6. 0g (94. 5mmol), dehydrated N,N--mercaptoacetamide (below), the gas in the flask was replaced with argon in a 300 mL flask. Called DMF) 120 mL at 120. (3) 4 hours after the reaction. After the reaction, the flask was cooled to room temperature (25 〇, the reaction solution was passed through a ruthenium column to remove insoluble components. Then, 5 〇〇mL of water was added, and the reaction product was extracted by gas-like extraction. After the oil layer of the chloroform solution was dried over magnesium sulfate, the oil layer was filtered to concentrate the crude liquid to obtain a crude product. The crude product was purified by using a solvent-purified Shixi rubber column to obtain 3.26 g of the compound 3. This operation was carried out. Several times. (Synthesis of Compound 4) 323941 37 201238994

In a flask in which the gas in the flask was replaced with argon gas, 10 g of 〇g (5.20 mmol) of compound 3 and tetrahydrofuran (hereinafter referred to as THF) was added to make a homogeneous solution. Keep the flask in the crucible. Thereafter, 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 1 wt.% by weight aqueous sodium thiosulfate solution and water. The resulting solid is referred to as Tanning 4-A. Then, 200 mL of a 1% by weight aqueous solution of sodium thiosulfate was added to the filtrate, followed by extraction by gas chromatography. The organic layer of the gas-like 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 material 4-B, and purified by a solvent-purified gas chromatography column chromatography to obtain 17 3 g of the compound 4. This operation is performed several times. (Synthesis of Compound 5)

In a 1,000 mL four-necked flask equipped with a mechanical stirrer and a gas in a flask instead of argon, 25·〇g (71. 4 mm〇1) of compound 4, 250 气 of gas, 160 mL of trifluoron was added. Acetic acid makes it a homogeneous solution. To the solution, sodium perborate hydrate hydrate 2i 〇g (210匪〇1) ' was added to the solution for 35 minutes at room temperature (25t:) for 24 minutes, and then, a 5% by weight aqueous solution of sodium sulfite was added to the reaction solution 201238994. After 500 mL, the reaction was stopped, and sodium carbonate was added until the pH of the reaction solution 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 a liquid, and the solvent of the mash was distilled off by an evaporator. The residue was recrystallized using decyl alcohol to give 7.70 g (21. Ommol) of Compound 5. This operation is performed several times. (Synthesis of Compound 6)

To a 2,000 mL flask in which the gas in the flask was replaced with argon, 23. lg (63.1 mmol) of Compound 5 and 1,500 mL of THF were added to make a homogeneous solution. The flask was cooled to -5 ° C, and 190 mL of a 1 mol /L solution of n-octylmagnesium bromide in THF was added dropwise over 10 minutes. After stirring the reaction solution at -50 ° C for 30 minutes, 50 mL of water was added to stop the reaction. The reaction solution was allowed to warm to room temperature (25 ° C), and THF 1, OOOrnL was distilled off with an evaporator, and then 100 mL of acetic acid was added. The reaction product was extracted by a gas chromatography, 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 compound 6 was obtained after drying under reduced pressure. (Synthesis of Compound 7)

323941 39 201238994 In a 100 mL four-necked flask in which the gas in the flask was replaced with argon, 1.00 g (4.80 mmol) of the compound 6 and 30 mL of dehydrated THF were added to make a homogeneous solution. While maintaining the flask at -20 ° C, 1 M 32.7 ml of a solution of 3,7-didecyloctylmagnesium bromide in diethyl 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 of the ethyl acetate solution was dried over sodium sulfate, and filtered, the ethyl acetate solution was passed through a silica gel column, and the solvent of the mixture was distilled off to obtain 1.50 g of Compound 7. 1H NMR in CDCI3 (ppm): 8.42 (b, 1H), 7.25 (d, 1H) > 7.20 (d.1H), 6. (d, 1H), e. 7β (<;ΜΗ), 2· 73(b*1H), 1, 90(γτκ4Η), 1. 58-1. 〇2(b, 2 〇H)%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, 50 g of Compound 7 and 30 mL of toluene were added to make a homogeneous solution. To the solution was added 100 mg of sodium p-Sodium sulfonate monohydrate at 1 Torr.匸 fell for 1.5 hours. After the reaction solution was cooled to room temperature (25 ° C), 5 mL of water was added thereto, and the reaction product was extracted with a nail. The organic 323941 40 201238994 layer of sodium sulphate solution was filtered, and the solvent was distilled off. The obtained crude product was purified by a silica gel column eluted with hexanes to afford 1.33 g of Compound 8. This operation is performed several times. 'H NMR In CDCI3 (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), 〇. 86(s, 1 2H) (synthesis of compound 9)

In a 200 mL flask in which the gas in the flask was replaced with argon, 2·16 § (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 〇c, and 2.37 mL (ll. 4 mmol) of the n-butyl chain of 2. After the completion of the dropwise addition, the reaction solution was stirred at -78 °C for 30 minutes, and then stirred at room temperature (25C) for 2 hours. The flask was then cooled to _78. (:, adding 4.07 g (12.5 imnol) of tributyltin chloride. After the addition, the mixture was stirred at _78 Torr for 3 Torr, and then, at room temperature (25 〇, the mixture was stirred for 3 hours. Then, 2 mL of water was added. ^ The reaction was stopped, and the reaction product was extracted with ethyl acetate. The organic layer of the solution of sodium sulphate sulphate was used as a solution, and the solvent was concentrated by evaporation in a solvent. The oily substance obtained by purifying the rubber column is used. (4) The column of the column is firstly immersed in hexane containing 5 weights of #% triethylamine 323941 201238994 for 5 minutes, and then washed with hexane. 52 g (3.34 mmol) of compound 9. Synthesis Example 2 (synthesis of compound 10)

10 Into a 500 mL flask, 10.2 g (70. 8 mmol) of 4,5-difluoro-1,2-diaminobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and 150 mL of a ratio of ° was adjusted to obtain a uniform solution. The flask was kept at 0 ° C, and sulfoxide gas 16. Og (134 mmol) 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. The organic layer of the solution was dried with sodium sulfate and dried overnight. The filtrate was concentrated by an evaporator to purify the precipitated solid by recrystallization. The solvent for recrystallization is methanol. After purification, 10.5 g (61.0 mmol) of Compound 10 was obtained. ^ NMR (CDCI3, ppm): 7.75 (t. 2H) 19F NMR (CDCI "ppm): -12S. 3 (3, 2F) (Synthesis of Compound 11)

323941 42 201238994 In a 100 mL flask, 2. OOg U1·6 mmol) of compound 10, 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 the completion of the dropwise addition, the mixture was stirred at 90 ° C for 38 hours. Then, after cooling the flask to room temperature (25 ° C), it was diluted with methanol to 100 mL. The obtained solution was poured into 300 mL of a 5% by weight 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 a gas. 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 give 1.50 g of Compound 11. 19F NMR (CDCI3, ppm): -118.9 (8, 2F) Synthesis Example 3 (Production of Polymer Compound A) 500 mg (0.475 mmol) of Compound 9, was added to a 200 mL flask in which the gas in the flask was replaced with argon gas. 141 mg (0.427 mmol) of compound 11 and 32 mL of toluene were used to make a homogeneous solution. The resulting sputum solution was bubbled with argon for 30 minutes. Then, 6.52 mg (0. 〇〇7 mmol) of tris(dibenzylideneacetone) dipalladium and 13. Omg of tris(2-indolylphenyl)phosphine are added to the benzene solution. c Stir 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 3 methanol. The precipitated polymer was filtered, and after the recovery, the obtained polymer was placed in a cylindrical filter paper, and subjected to extraction with 323941 43 201238994 by a Soxhlet extractor for 5 hours using decyl alcohol, acetone and hexane, respectively. 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 5 mL of a 3% by weight aqueous acetic acid solution, followed by washing twice with 5 mL of water, followed by washing twice with 5% fluorinated aqueous solution 5 mL, followed by washing twice. After washing twice with 50 mL of water, the resulting solution was poured into methanol to precipitate a polymer. The polymer was filtered, dried, and the obtained polymer was redissolved in 50 mL of o-dibenzene and passed through an alumina/ruthenium tube 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. S S V-SnBua

The polymer compound A has the following repeating unit. In the formula, η represents the number of repeating units.

323941 44 201238994 Production of Example K Organic Photoelectric Conversion Element) A 玻璃0-patterned glass substrate, a film thickness of about 15 Å, which is formed by a sputtering method, is washed with an organic solvent, an alkali detergent, and ultrapure water, and then dried. . Ultraviolet odor (UV-〇3) treatment was applied to the glass plate using a UV-money (UV_〇3) device. , 禋〇 禋〇 5 5 m filter, filter the poly (3, 4) Ethyloxy thiophene / polystyrene sulfonic acid suspension s 忱 Kk dissolved in water to worry about ytr 〇 n P Τρ AI 4083). The filtered suspension was spin-coated on the IT0 side of the substrate to form a film having a thickness of 7 Å. Next, it was dried in the atmosphere for 20 minutes in the atmosphere for 1 minute to form an organic layer. . Receiver, will be adjacent - two gas stupid (SP value: 2 〇. 72 (J / cm3) 1/2, boiling point: 183. 〇 and gas simulation (SP value: 18 81 (J / cm3) 1/2, boiling point :6im Kunming, a mixed solution having a weight of 85:15. Then, a polymer compound A and [6,6]-stupyl C71 were added to the mixed solution in such a manner that the weight ratio was 1.2. - a coating solvent is prepared by adding methyl vinegar ([6,6]_phenyl cn_b ^ 曰 曰 ester methyl ester). The amount of the same molecular compound A added is 0.5% by weight relative to the mixed solvent = heavy. The weight average molecular weight of the polystyrene converted to the molecular compound A was 29,000, and the number average molecular weight of the polystyrene was 14 and the wavelength of the light absorption end of the polymer compound A was 89 〇 nm. In the coating solution, the number of rotations of 黯 pm to 1 () 〇〇 _ is performed and mixed. _ Mixing is performed on the heating (4) 11 of the variable temperature function. The set temperature is 70. 〇 Then, the aperture is 0.5" filtered H-sewed fabric, which is coated on the 323941 45 201238994 organic layer and then dried in a nitrogen atmosphere to form The layer is formed in a resistive heating vapor deposition apparatus such that the film thickness of LiF is about 2·3 ηηη on the active layer, and then A1 is formed into a film thickness of about 70 nm, that is, an electrode is formed. The rapid hardening type Araldite was subjected to a sealing treatment as a sealant, and the glass substrate was subsequently subjected to an organic thin tantalum solar cell. Comparative Example 1 (Production of Organic Photoelectric Conversion Element) In addition to the use of o-dichlorobenzene in a coating solvent to replace the adjacent An organic photoelectric conversion element was produced in the same manner as in Example 1 except that the mixed solution of the second gas and the gas was mixed. (Evaluation of photoelectric conversion efficiency) Organic photoelectric conversion elements obtained in Example 1 and Comparative Example 1 The shape of the organic thin film solar cell is a square of 2 mm x 2 min. These organic thin film solar cells use a solar simulator (S〇iar Simulator) (product name: CEP-2000 type, illuminance l〇〇) mW/cm2) After a certain amount of light is irradiated, the generated current and voltage are measured, and the photoelectric conversion efficiency can be calculated. The results are shown in Table 1. [Table 1] Solvent in the coating solution Photoelectric conversion efficiency (%) Example 1 o-di-benzene and gas-like 6.72 Comparative Example 1 o-di-lactic benzene 6.54 [Probability of industrial application] Photoelectricity can be produced by applying the production method of the present invention The organic photoelectric conversion element which is excellent in conversion efficiency. 323941 46 201238994 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a layer configuration of an organic photoelectric conversion element in the production method of the present invention. 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. [Main component symbol description] 0 Organic photoelectric conversion element 20 Substrate 32 34 40 42 44 52 54 First electrode Second electrode Active layer First active layer Second active layer First intermediate layer Second intermediate layer 323941 47

Claims (1)

201238994 VII. Patent application scope: 1. In the method for producing an organic photoelectric conversion device comprising an active layer containing a polymer compound between the counter electrode, the polymer compound has a structural unit represented by the formula (1), and the active layer may contain a polymer compound, a first solvent, and the first A solution of a second solvent having a different solvent is formed. [wherein] Ar1 and Ar2 may be the same or different and each represents a trivalent aromatic group; 1^, 1^, 1^3, 1^4, 1^5, 1^, 1^ and 1^ may be the same or different and represent a hydrogen atom, a dentate atom, an alkyl group, an alkoxy group, or an alkylthio group. , aryl, aryloxy, arylthio, aralkyl, aralkoxy, aralkylthio, fluorenyl, decyloxy, decylamino, quinone imine, imine, amine, substituted Amine, substituted fluorenyl, substituted fluorenyloxy, substituted fluorenylthio, substituted fluorenylamino, monovalent heterocyclic, heterocyclic oxy, heterocyclic thio, aralkenyl, aralkynyl, carboxy Or cyano; η means 1 or 2; if η is 2, 2 Z may be the same or different]. 2. The method according to claim 1, wherein the polymer compound is a polymer compound further containing any one of the structural units of the following formulas (2-1) to (2-10). 323941 1 201238994 Vi; 'R21 to R<2 are independent of each other to represent hydrogen atom 3 =]'. To x is an independent representation of the sulfur atom 'oxygen source'; as in the scope of the patent application, the item is a higher compound of the structural unit represented by the formula (2). 323941 201238994 At least one of them is a nitrogen atom. 7. If the patent application is in the first place, it is a nitrogen atom. The method of claim 3, wherein χΙ is the same as X1. 8. For example, the third or oxygen atom of the patent application. The method described in the item, wherein: ¥1 is a sulfur atom. 9.= The method described in item i of the range of materials, wherein, the first! The solvent is a cubic chlorine compound, and the second solvent is an aliphatic chlorine compound. Apply for patent coverage! A method for producing an organic photoelectric conversion element comprising an active layer of a pair of electrodes 2 between a pair of electrodes, comprising coating a polymer compound, a first solvent, and a different electrode on a square electrode The step of forming an active layer by the liquid of the second solvent of the solvent W and the step of forming another electrode on the active layer. 11. An organic photoelectric conversion element which can be manufactured by the method described in the scope of the patent application. -Ar2·-Ar1-Vz-fn - a liquid containing a polymer compound containing a structural unit represented by the formula (1), a first solvent and a second solvent different from the first solvent, 3 1 , Ar2 and Ar1 may be the same or different and represent a trivalent aromatic group; Z represents -〇-, -s-, -c〇〇)-, -CRiR2_, _s(=〇)__, _s〇2_, 2 201238994 Oxy, amidino, quinone imino, imino, amine, substituted amine, substituted fragment, substituted aryloxy, substituted arylthio, substituted amide, monovalent heterocycle Or a heterocyclic oxy group, a heterocyclic thio group, an aralkenyl group, an arylalkynyl group, a carboxy group or a cyano group; η represents 1 or 2; when η is 2, 2 Z may be the same or different]. 13. The liquid according to claim 12, wherein the polymer compound contains, in addition to the structural unit represented by the formula (1), any one of the formulae (2-1) to (2-10). Repeating unit of polymer compound, In the formulae (2-1) to (2-10), R21 to R42 each independently represent a hydrogen atom or a substituent; and X21 to Χ3() each independently represent a sulfur atom, an oxygen atom or a ruthenium atom]. 14. The liquid according to claim 12, wherein the polymer compound contains a polymer compound of a structural unit represented by the formula (2) in addition to the structural unit represented by the formula (1). 323941 4 201238994 [wherein, X1 and 丫2_^ are sulphur II: the same or different 'is a gas atom or, I m R ^ atom, a base atom - n (r43) h4 < r, w1 and not a cashmere or Substituent; identical or different, meaning having a cyano group, a fluoroorganic group, a self-priming atom or a hydrogen atom]. The valence of the mouse atom is as follows: 1. The liquid of the polymer compound 1 1 in the table = structural unit and the second solvent in the first and the granules. 16. For the liquid described in item 12 of the special (4), which contains a high compound containing the structural unit represented by the formula (1) and the structural unit represented by the formula (2), the 帛1 solvent is different from the first! The second solvent of the solvent, -Ar1-Ar2-(1) wn [wherein, Ar and Ar may be the same or different, and represent a trivalent aromatic group; Z represents -〇-, -s-, -c(=〇 )_, _cr1r2_, _s(=〇)_, _s〇2, ~Si(R3)(R4)— !^, 1^, 1^, 1^, 1^, 1^, 1^ and ^ can be the same Or different, meaning hydrogen atom, ® atom, alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aralkylthio, fluorenyl , anthraceneoxy, amidino, oximine, imine, amine, substituted amine, substituted fluorenyl, substituted fluorenyloxy, substituted fluorenylthio, substituted fluorenylamino, monovalent a cyclic group, a heterocyclic oxy group, a heterocyclic thio group, an aralkenyl group, an aralkynyl group, a aryl group or a cyano group, n 疋 represents 1 or 2; if η is 2, 2 Z may be the same or different] , 323941 201238994 (2) wherein X1 and X2 may be the same or different and represent a nitrogen atom or =CH-; Y1 represents a sulfur atom, an oxygen atom, a selenium atom, -N(R43)- or -CR44=CR 45-; R43 R44 and R45 may be the same or different and represent a hydrogen atom or a substituent; W1 and W2 may be the same or different and each represents a valent group, a fluorine atom or a halogen atom or a hydrogen atom] 323941 6