JP2011060881A - Material for photovoltaic element and photovoltaic element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photovoltaic element high in photoelectric conversion efficiency. <P>SOLUTION: There are provided a material for the photovoltaic element including an electron-donating organic material having a specified structure, and a photovoltaic element using the material. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photovoltaic element material and a photovoltaic element using the same.

  Solar cells are attracting attention as an environmentally friendly electrical energy source and an influential energy source for increasing energy problems. Currently, inorganic materials such as single crystal silicon, polycrystalline silicon, amorphous silicon, and compound semiconductors are used as semiconductor materials for photovoltaic elements of solar cells. However, solar cells manufactured using inorganic semiconductors have not been widely used in ordinary households because of high costs compared with power generation methods such as thermal power generation and nuclear power generation. The high cost factor is mainly in the process of manufacturing a semiconductor thin film under vacuum and high temperature. Therefore, organic solar cells using organic semiconductors and organic dyes such as conjugated polymers and organic crystals are being studied as semiconductor materials expected to simplify the manufacturing process.

  However, an organic solar cell using a conjugated polymer or the like has the biggest problem that the photoelectric conversion efficiency is lower than that of a conventional solar cell using an inorganic semiconductor, and has not yet been put into practical use. The photoelectric conversion efficiency of organic solar cells using conventional conjugated polymers is mainly due to the low solar absorption efficiency and the excitons that are difficult to separate the electrons and holes generated by sunlight. This is because a state is formed and a trap for trapping carriers (electrons and holes) is easily formed, so that the generated carriers are easily trapped in the trap and the mobility of carriers is slow.

  Conventional photoelectric conversion elements using organic semiconductors can be generally classified into the following element configurations at present. A Schottky type that joins an electron-donating organic material (p-type organic semiconductor) and a metal having a low work function, and an electron-accepting organic material (n-type organic semiconductor) and an electron-donating organic material (p-type organic semiconductor). Heterojunction type. In these elements, only the organic layer (about several molecular layers) at the junction contributes to the photocurrent generation, so that the photoelectric conversion efficiency is low, and its improvement is a problem.

As a method for improving photoelectric conversion efficiency, a bulk heterojunction in which an electron-accepting organic material (n-type organic semiconductor) and an electron-donating organic material (p-type organic semiconductor) are mixed to increase the bonding surface contributing to photoelectric conversion There is a type (for example, see Non-Patent Document 1). Among them, the conjugated polymer used as the electron donating organic material (p-type organic semiconductor), a fullerene or a carbon nanotube, such as other C ₆₀ of the conductive polymer having the semiconductor characteristics of the n-type as the electron accepting organic material The used photoelectric conversion material is reported (for example, refer nonpatent literatures 2-3 and patent documents 1-2).

  In addition, in order to increase the carrier mobility of the electron-donating organic material (p-type organic semiconductor) and improve the photoelectric conversion efficiency, a conjugated polymer incorporating a highly planar polycyclic condensed π-conjugated molecule has been reported. (For example, refer nonpatent literature 4-5.). However, sufficient photoelectric conversion efficiency has not been obtained.

JP 2003-347565 A (Claims 1 and 3) JP 2004-165474 A (Claims 1 and 3)

J. et al. J. et al. M.M. Halls, C.I. A. Walsh, N .; C. Greenham, E.I. A. Marsegla, R.M. H. Frind, S.M. C. Moratti, A.M. B. Homes, "Nature", 1995, 376, 498 E. Kymakis, G .; A. J. et al. Amaruntunga, "Applied Physics Letters" (USA), 2002, 80, 112. G. Yu, J. et al. Gao, J .; C. Hummelen, F.M. Wudl, A.W. J. et al. Heeger, "Science", 1995, 270, 1789 S. Cho, J. et al. H. Seo, S. H. Kim, S.M. Song, Y .; Jin, K .; Lee, H.C. Suh, A .; J. et al. Heeger, “Applied Physics Letters”, 2008, 93, 263301. S. Song, Y .; Jin, S .; H. Kim, J. et al. Moon, K. Kim, J. et al. Y. Kim, S.M. H. Park, K.M. Lee, H.C. Suh, "Macromolecules", 2008, 41, 7296

  As described above, all of the conventional organic solar cells have a problem of low photoelectric conversion efficiency. An object of this invention is to provide a photovoltaic device with high photoelectric conversion efficiency.

  The present invention is a photovoltaic device material containing an electron donating organic material having a structure represented by the general formula (1) or (2), and a photovoltaic device using the material.

In the general formula (1), X ¹ and X ² may be the same or different and each represents silicon, phosphorus or nitrogen. R ^{1 to} R ⁴ in the general formula (1) and R ¹ and R ³ in the general formula (2) may be the same as or different from each other, and are hydrogen, alkyl group, alkoxy group, aryl group, heteroaryl. Selected from the group halogen. However, when X ¹ and X ² are trivalent phosphorus or nitrogen, R ² and R ⁴ are not present. In the above general formulas (1) to (2), ring B, ring C and ring D represent an optionally substituted aryl ring or heteroaryl ring. A represents a single bond or a divalent linking group. m represents the range of 0-10. n represents a range of 2 or more and 1,000 or less.

  According to the present invention, a photovoltaic device with high photoelectric conversion efficiency can be provided.

The schematic diagram which showed the one aspect | mode of the photovoltaic device of this invention. The schematic diagram which showed another aspect of the photovoltaic element of this invention.

  The photovoltaic element material of the present invention includes an electron donating organic material having a polycyclic condensed structure represented by the general formula (1) or the general formula (2).

In the general formula (1), X ¹ and X ² may be the same or different, and represent a hetero atom of silicon, phosphorus or nitrogen. In order to improve the photoelectric conversion efficiency by lowering the HOMO (highest occupied molecular orbital) level of the electron donating organic material and increasing the open circuit voltage (Voc) of the photovoltaic element, X ¹ and X ² must be phosphorus. It is preferable that In order to lower the HOMO level of the organic material, it is more preferable to adopt a pentavalent phosphorus structure represented by the general formula (2). On the other hand, silicon and nitrogen can increase the carrier mobility of the electron-donating organic material as compared with the carbon atom, so that the photoelectric conversion efficiency can be improved. In particular, a pi-conjugated compound containing silicon can further increase the carrier mobility of the electron-donating organic material due to the interaction effect between the antibonding sigma orbital of silicon and the antibonding pi orbital of adjacent carbon. In order to further increase the conversion efficiency, silicon is more preferably used.

In the general formulas (1) to (2), R ^{1 to} R ⁴ may be the same or different and are selected from hydrogen, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, and a halogen. However, when X ¹ and X ² are trivalent phosphorus or nitrogen, R ² and R ⁴ are not present. When X ¹ and X ² are pentavalent phosphorus, R ² and R ⁴ do not exist, and as represented by the general formula (2), there are two oxygen atoms between X ¹ and X ^2. A double bond is formed.

  Here, the alkyl group is, for example, a saturated aliphatic group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group. The hydrocarbon group may be linear, branched, or cyclic, and may be unsubstituted or substituted. Examples of the substituent when substituted include the following alkoxy groups, aryl groups, heteroaryl groups, and halogens. The number of carbon atoms in the alkyl group is preferably 4 or more when the solubility of the organic material is increased and applied to a wet process such as spin coating, and 12 or less in order to maintain sufficient carrier mobility of the organic material. It is preferable that

  The alkoxy group refers to, for example, an aliphatic hydrocarbon group via an ether bond such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. Absent. Examples of the substituent when substituted include the following aryl groups, heteroaryl groups, and halogens. The preferable carbon number range of the alkoxy group is the same as that of the alkyl group described above.

  The aryl group represents, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, an anthryl group, a terphenyl group, a pyrenyl group, a fluorenyl group, and a perylenyl group, which is unsubstituted. But it can be replaced. Examples of the substituent in the case of substitution include the above alkyl group, alkoxy group, the following heteroaryl group, and halogen. The number of carbon atoms of the aryl group is preferably 6 or more and 12 or less when applied to a wet process.

  The heteroaryl group is, for example, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, oxazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolinyl group, isoquinolyl group, quinoxalyl group, acridinyl group, indolyl group. A heteroaromatic ring group having an atom other than carbon, such as a group, a carbazolyl group, a benzofuran group, a dibenzofuran group, a benzothiophene group, a dibenzothiophene group, a benzodithiophene group, a silole group, a benzosilole group, and a dibenzosilole group; May be unsubstituted or substituted. Examples of the substituent in the case of substitution include the above alkyl group, aryl group, and the following halogen. The carbon number of the heteroaryl group is preferably 2 or more and 10 or less when applied to a wet process.

  The halogen is any one of fluorine, chlorine, bromine and iodine.

In the general formulas (1) to (2), from the viewpoint of ease of synthesis, R ^{1 to} R ⁴ are preferably an alkyl group or an aryl group.

  In the above general formulas (1) to (2), ring B, ring C and ring D represent an optionally substituted aryl ring or heteroaryl ring. Examples of the aryl ring include the aromatic rings exemplified for the aryl group, and examples of the heteroaryl ring include the heteroaromatic rings exemplified for the heteroaryl group. When the rings B to D are substituted, the substituent is preferably an electron-withdrawing group such as fluorine, and can lower the HOMO level of the organic material. In particular, fluorine is more preferably used because it has a small atomic radius and suppresses twisting of the polymer chain to keep the carrier mobility of the electron-donating organic material high. On the other hand, an alkoxy group is preferably used from the viewpoint of synthesis that facilitates derivatization of the monomer. Further, from the viewpoint of ease of synthesis, the ring B, ring C and ring D are preferably benzene rings which may be substituted.

  Among the structures represented by the above general formula (1) or general formula (2), examples of polycyclic condensed structures from -ring B to ring D- excluding A from the repeating unit structure include the following structures: Is mentioned.

  In the general formulas (1) to (2), A represents a single bond or a divalent linking group. In order to extend the electron conjugated system of the electron donating organic material and increase the carrier mobility, it is preferable that A has an arylene group or a heteroarylene group. Examples of the linking group A are not particularly limited, and specifically include m-phenyl, p-phenyl, biphenyl, terphenyl, quarterphenyl, naphthyl, anthran, pyrene, benzothiophene, dibenzothiophene, and indole. , Carbazole, fluorene, dibenzosilol, cyclopentadithiophene and the like.

  In order to absorb radiant energy over a wide range of the sunlight spectrum, it is desirable to narrow the band gap of the electron-donating organic material, and this narrowing of the organic material includes nitrogen-containing materials such as benzothiadiazole and quinoxaline. It is known that it is effective to incorporate heteroarylene having a double bond into a material (for example, Non-Patent Document, J. Roncail, “Macromolecular Rapid Communications”, 2007, 28, page 1761). In the general formulas (1) to (2), the linking group A more preferably includes a condensed heteroarylene structure having such a nitrogen-containing double bond. Examples of the linking group A including a condensed heteroarylene structure having a nitrogen-containing double bond include the following structures.

  In the general formulas (1) to (2), m represents a range of 0 or more and 10 or less. From the viewpoint of ease of synthesis, m is preferably in the range of 0 or more and 2 or less.

  In the above general formulas (1) to (2), n represents the degree of polymerization and represents a range of 2 or more and 1,000 or less. By setting n to 2 or more, an effective carrier path can be formed in the aforementioned bulk heterojunction thin film, so that the photoelectric conversion efficiency can be increased. In order to form an excellent carrier path, n is preferably 5 or more, and preferably less than 100 for ease of synthesis. The degree of polymerization can be determined from the weight average molecular weight. The weight average molecular weight can be determined by measuring using GPC (gel permeation chromatography) and converting to a polystyrene standard sample.

  Specific examples of the electron-donating organic material having the structure represented by the general formula (1) or the general formula (2) include the following structures. However, n shows the range of 2 or more and 1,000 or less.

Note that the electron-donating organic material having the structure represented by the general formula (1) or the general formula (2) can be synthesized by a known method. First, among the structures represented by the general formula (1) or the general formula (2), a polycyclic condensed molecule from -ring B to ring D- excluding A from the repeating unit structure is, for example, X ¹ and when X ² is silicon, it can be synthesized by the method described JP 2006-253230, JP 2007-119392, JP 2007-2999980 and JP Patent 2008-156261. In the case of phosphorus, it can be synthesized by the method described in Japanese Patent Application Laid-Open No. 2008-56639, and in the case of nitrogen, the method described in Chemical Physics, 1997, 216, 179-192. Next, oligomers and polymers having a structure represented by the general formula (1) or the general formula (2) are described in, for example, “Advanced Functional Materials”, 2007, Vol. 17, pages 3836-3842. Or “Macromolecules”, 2004, 37, 8978-8983, and can be synthesized by a method similar to that described in “Macromolecules”.

The photovoltaic device material of the present invention may be composed only of an electron-donating organic material having a structure represented by the general formula (1) or (2), or other electron-donating organic material. May be included. Examples of other electron-donating organic materials include polythiophene polymers, benzothiadiazole-thiophene derivatives, benzothiadiazole-thiophene copolymers, poly-p-phenylene vinylene polymers, poly-p-phenylene polymers. Conjugated polymers such as polymers, polyfluorene polymers, polypyrrole polymers, polyaniline polymers, polyacetylene polymers, polythienylene vinylene polymers, H ₂ phthalocyanine (H ₂ Pc), copper phthalocyanine ( CuPc), phthalocyanine derivatives such as zinc phthalocyanine (ZnPc), porphyrin derivatives, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine ( TPD), N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl Triarylamine derivatives such as -1,1'-diamine (NPD), carbazole derivatives such as 4,4'-di (carbazol-9-yl) biphenyl (CBP), oligothiophene derivatives (terthiophene, quarterthiophene, And low molecular organic compounds such as cithiophene and octithiophene).

  The electron donating organic material having the structure represented by the general formula (1) or the general formula (2) is a material exhibiting p-type semiconductor characteristics, and the photovoltaic device material of the present invention has higher photoelectric conversion efficiency. It is preferable to combine with an electron-accepting organic material (n-type organic semiconductor) in order to obtain the above.

The electron-accepting organic material used in the present invention is an organic material exhibiting n-type semiconductor characteristics. For example, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), 3,4,9,10 -Perylenetetracarboxylic dianhydride (PTCDA), 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), N, N'-dioctyl-3,4,9,10-naphthyltetracarboxydiimide ( PTCDI-C8H), 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBD), 2,5-di (1-naphthyl) -1, Oxazole derivatives such as 3,4-oxadiazole (BND), 3- (4-biphenylyl) -4-phenyl-5- (4-t - butylphenyl) -1,2,4-triazole (triazole derivatives such as TAZ), phenanthroline derivatives, phosphine oxide derivatives, fullerene compounds _{(C 60, C 70, C} 76, C 78, C 82, C 84, C 90 , C ₉₄ and the like, [6,6] -phenyl C61 butyric acid methyl ester ([6,6] -PCBM), [5,6] -phenyl C61 butyric acid methyl ester ( [5,6] -PCBM), [6,6] -phenyl C61 butyric acid hexyl ester ([6,6] -PCBH), [6,6] -phenyl C61 butyric acid dodecyl ester ([6,6 ] -PCBD), phenyl C71 butyric acid methyl ester _(PC 70 BM), phenylene C85, such as butyric acid methyl ester _(PC 84 BM)), carbon nanotubes (CNT), poly -p- phenylene vinylene-based polymer derivatives obtained by introducing cyano group into (CN-PPV) and the like. Among these, fullerene compounds are preferably used because of their high charge separation speed and electron transfer speed. Among fullerene compounds, C ₇₀ derivatives (such as the above PC ₇₀ BM) are more preferable because they are excellent in light absorption characteristics and can obtain higher photoelectric conversion efficiency.

  In the photovoltaic device material of the present invention, the content ratio (weight fraction) of the electron-donating organic material and the electron-accepting organic material is not particularly limited. The rate is preferably in the range of 1 to 99:99 to 1, more preferably in the range of 10 to 90:90 to 10, still more preferably in the range of 20 to 60:80 to 40. The electron-donating organic material and the electron-accepting organic material may be used as a mixture or laminated. Although it does not specifically limit as a mixing method, After adding to a solvent in a desired ratio, the method of making it melt | dissolve in a solvent combining 1 type or multiple types of methods, such as a heating, stirring, and ultrasonic irradiation, is mentioned. . As will be described later, when the photovoltaic element material forms a single organic semiconductor layer, the above-mentioned content ratio is the content ratio of the electron-donating organic material and the electron-accepting organic material contained in the single layer. When the organic semiconductor layer has a laminated structure of two or more layers, it means the content ratio of the electron donating organic material and the electron accepting organic material in the whole organic semiconductor layer.

  In order to further improve the photoelectric conversion efficiency, it is preferable to remove impurities that can trap carriers as much as possible. In the present invention, the electron-donating organic material having the structure represented by the general formula (1) or the general formula (2) and the method for removing impurities from the electron-accepting organic material are not particularly limited. A graphic method, a recrystallization method, a sublimation method, a reprecipitation method, a Soxhlet extraction method, a molecular weight fractionation method by GPC, a filtration method, an ion exchange method, a chelate method and the like can be used. In general, a column chromatography method, a recrystallization method, and a sublimation method are preferably used for purification of a low molecular weight organic material. On the other hand, for purification of high molecular weight compounds, reprecipitation method, Soxhlet extraction method, molecular weight fractionation method by GPC is preferably used when removing low molecular weight components, and reprecipitation method or the like when removing metal components. A chelate method or an ion exchange method is preferably used. A plurality of these methods may be combined.

  Next, the photovoltaic element of the present invention will be described. The photovoltaic device of the present invention has at least a positive electrode and a negative electrode, and includes the photovoltaic device material of the present invention between them. FIG. 1 is a schematic view showing an example of the photovoltaic element of the present invention. In FIG. 1, reference numeral 1 is a substrate, reference numeral 2 is a positive electrode, reference numeral 3 is an organic semiconductor layer containing the photovoltaic element material of the present invention, and reference numeral 4 is a negative electrode.

  The organic semiconductor layer 3 contains the photovoltaic element material of the present invention. That is, the electron-donating organic material having a structure represented by the general formula (1) or the general formula (2) is included. When the photovoltaic element includes an electron donating organic material and an electron accepting material, these materials may be mixed or laminated, but are preferably mixed. That is, a bulk heterojunction photovoltaic device that increases the bonding surface contributing to photoelectric conversion by mixing an electron-donating organic material and an electron-accepting organic material is preferable. When they are mixed, the electron-donating organic material having the structure represented by the general formula (1) or the general formula (2) and the electron-accepting organic material are compatible at the molecular level or phase-separated. However, it is preferable that phase separation is performed at a nanometer size. The domain size of this phase separation structure is not particularly limited, but is usually 1 nm or more and 50 nm or less. When the electron donating organic material and the electron accepting organic material are laminated, the layer having the electron donating organic material exhibiting p-type semiconductor characteristics is on the positive electrode side, and the electron accepting organic material exhibiting n-type semiconductor characteristics It is preferable that the layer having a negative electrode side. An example of the photovoltaic element in the case where the organic semiconductor layer 3 is laminated is shown in FIG. Reference numeral 5 is a layer having an electron-donating organic material having a structure represented by the general formula (1) or (2), and reference numeral 6 is a layer having an electron-accepting organic material. The organic semiconductor layer preferably has a thickness of 5 nm to 500 nm, more preferably 30 nm to 300 nm. When laminated, the layer having the electron-donating organic material of the present invention preferably has a thickness of 1 nm to 400 nm, more preferably 15 nm to 150 nm.

  The organic semiconductor layer 3 includes an electron donating organic material having a structure represented by the general formula (1) or the general formula (2), and an electron donating organic material other than the electron accepting organic material (p-type organic semiconductor). ) May be included. Examples of the electron donating organic material (p-type organic semiconductor) used here include those exemplified above as other compounds of the electron donating organic material.

In the photovoltaic device of the present invention, it is preferable that either the positive electrode 2 or the negative electrode 4 has light transmittance. The light transmittance of the electrode is not particularly limited as long as incident light reaches the organic semiconductor layer 3 and an electromotive force is generated. Here, the light transmittance in the present invention is a value obtained by [transmitted light intensity (W / m ² ) / incident light intensity (W / m ² )] × 100 (%). The thickness of the electrode may be in a range having light transparency and conductivity, and is preferably 20 nm to 300 nm, although it varies depending on the electrode material. The other electrode is not necessarily light-transmitting as long as it has conductivity, and the thickness is not particularly limited.

  As an electrode material, it is preferable to use a conductive material having a high work function for one electrode and a conductive material having a low work function for the other electrode. An electrode using a conductive material having a large work function is a positive electrode. Conductive materials with a large work function include metals such as gold, platinum, chromium and nickel, transparent metal oxides such as indium, tin and molybdenum, and composite metal oxides (indium tin oxide (ITO)). Indium zinc oxide (IZO) and the like are preferably used. Here, the conductive material used for the positive electrode 2 is preferably one that is in ohmic contact with the organic semiconductor layer 3. Furthermore, when a hole transport layer described later is used, it is preferable that the conductive material used for the positive electrode 2 is in ohmic contact with the hole transport layer.

  An electrode using a conductive material with a low work function is a negative electrode, but as the conductive material with a low work function, alkali metal or alkaline earth metal, specifically lithium, magnesium, calcium, etc. are used. . Tin, silver, and aluminum are also preferably used. Furthermore, an electrode made of an alloy made of the above metal or a laminate of the above metal is also preferably used. Further, it is possible to improve the extraction current by introducing a metal fluoride such as lithium fluoride or cesium fluoride into the interface between the negative electrode 4 and the electron transport layer. Here, the conductive material used for the negative electrode 4 is preferably one that is in ohmic contact with the organic semiconductor layer 3.

  The substrate 1 is a substrate on which an electrode material and an organic semiconductor layer can be laminated according to the type and application of the photoelectric conversion material, for example, inorganic materials such as alkali-free glass and quartz glass, polyester, polycarbonate, polyolefin, polyamide, polyimide, polyphenylene A film or plate produced by an arbitrary method from an organic material such as sulfide, polyparaxylene, epoxy resin or fluorine resin can be used. When light is incident from the substrate side and used, it is preferable that each substrate described above has a light transmittance of about 80%.

In the present invention, a hole transport layer may be provided between the positive electrode 2 and the organic semiconductor layer 3. As a material for forming the hole transport layer, conductive polymers such as polythiophene polymers, poly-p-phenylene vinylene polymers, polyfluorene polymers, phthalocyanine derivatives (H ₂ Pc, CuPc, ZnPc, etc.) ), Low molecular organic compounds exhibiting p-type semiconductor properties such as porphyrin derivatives are preferably used. In particular, polyethylenedioxythiophene (PEDOT), which is a polythiophene polymer, or PEDOT to which polystyrene sulfonate (PSS) is added is preferably used. The thickness of the hole transport layer is preferably 5 nm to 600 nm, more preferably 30 nm to 200 nm. In order to further improve the photoelectric conversion efficiency, the hole transport layer is preferably treated with a fluorous compound (an organic compound having one or more fluorine atoms in the molecule). Examples of the fluorous compound include benzotrifluoride, hexafluorobenzene, 1,1,1,3,3,3-hexafluoro-2-propanol, perfluorotoluene, perfluorodecalin, perfluorohexane, 1H, 1H, 2H, 2H- Examples include heptadecafluoro-1-decanol (F-decanol). More preferably, benzotrifluoride, perfluorohexane, or F-decanol is used. As a treatment method, the above-mentioned fluorous compound is previously mixed with the material for forming the hole transport layer, and then the hole transport layer is formed, or the hole transport layer is formed and then the above-mentioned fluoro compound is brought into contact with the material. Examples of the method include spin coating, dip coating, blade coating, vapor deposition, and steam treatment.

  In the photovoltaic device of the present invention, an electron transport layer may be provided between the organic semiconductor layer 3 and the negative electrode 4. The material for forming the electron transport layer is not particularly limited, but the above-described electron-accepting organic materials (NTCDA, PTCDA, PTCDI-C8H, oxazole derivatives, triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, fullerene compounds, An organic material exhibiting n-type semiconductor characteristics such as CNT and CN-PPV is preferably used. The thickness of the electron transport layer is preferably 5 nm to 600 nm, more preferably 30 nm to 200 nm.

  In the photovoltaic device of the present invention, two or more organic semiconductor layers may be stacked (tandemized) via one or more intermediate electrodes to form a series junction. For example, a laminated structure of substrate / positive electrode / first organic semiconductor layer / intermediate electrode / second organic semiconductor layer / negative electrode can be given. By laminating in this way, the open circuit voltage can be improved. Note that the hole transport layer described above may be provided between the positive electrode and the first organic semiconductor layer and between the intermediate electrode and the second organic semiconductor layer, and between the first organic semiconductor layer and the intermediate electrode. The hole transport layer described above may be provided between the second organic semiconductor layer and the negative electrode.

In the case of such a laminated structure, at least one of the organic semiconductor layers contains the material for a photovoltaic device of the present invention, and the other layers have the general formula (1) or the general formula in order not to reduce the short-circuit current. The electron donating organic material having a structure represented by (2) preferably contains an electron donating organic material having a different band gap. Examples of such an electron-donating organic material include the polythiophene polymer, poly-p-phenylene vinylene polymer, poly-p-phenylene polymer, polyfluorene polymer, polypyrrole polymer, polyaniline described above. Polymer, polyacetylene polymer, polythienylene vinylene polymer, benzothiadiazole polymer (for example, PCPDTBT (poly [2,6- (4,4-bis- (2-ethylhexyl) -4H-cyclopenta [ 2,1-b; 3,4-b ′] dithiophene) -alt-4,7- (2,1,3-benzothiadiazole)]) and PSBTBT (poly [(4,4-bis- (2-ethylhexyl)). ) Dithino [3,2-b: 2 ′, 3′-d] silole) − , 6-diyl-alt- (2,1,3 -benzothiadiazole) -4,7-diyl])) conjugated polymer or, _{H 2} phthalocyanine such as _(H 2 Pc), copper phthalocyanine (CuPc), zinc phthalocyanine Phthalocyanine derivatives such as (ZnPc), porphyrin derivatives, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine (TPD), N, Triarylamine derivatives such as N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl-1,1′-diamine (NPD), 4,4′-di (carbazol-9-yl) biphenyl ( Carbazole derivatives such as CBP), oligothiophene derivatives (terthiophene, quarterthiophene, sexithiophene, octithiophene, etc. Low molecular organic compounds and the like. In addition, as the material for the intermediate electrode used here, a material having high conductivity is preferable. For example, the above-described metals such as gold, platinum, chromium, nickel, lithium, magnesium, calcium, tin, silver, and aluminum, Metal oxides such as indium, tin, and molybdenum, composite metal oxides (indium tin oxide (ITO), indium zinc oxide (IZO), etc.), alloys composed of the above metals, and laminates of the above metals , Polyethylenedioxythiophene (PEDOT), and those obtained by adding polystyrene sulfonate (PSS) to PEDOT. The intermediate electrode is preferably light transmissive, but even a material such as a metal having low light transmissive properties can often ensure sufficient light transmissive properties by reducing the film thickness.

  Next, an example is given and demonstrated about the manufacturing method of the photovoltaic device of this invention. A transparent electrode such as ITO (corresponding to a positive electrode in this case) is formed on the substrate by sputtering or the like. Next, the photoelectric conversion element material containing the electron-donating organic material having the structure represented by the general formula (1) or the general formula (2) and, if necessary, the electron-accepting organic material is dissolved in a solvent to obtain a solution. The organic semiconductor layer is formed by applying on the transparent electrode. The solvent used at this time is preferably an organic solvent. For example, methanol, ethanol, butanol, toluene, xylene, o-chlorophenol, acetone, ethyl acetate, ethylene glycol, tetrahydrofuran, dichloromethane, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, Examples include chlorobenzene, chloronaphthalene, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and γ-butyrolactone. Two or more of these may be used. Moreover, photoelectric conversion efficiency can be improved more by containing the above-mentioned fluorous compound. Fluorous compounds (fluorus solvents) that are liquid at normal temperature and pressure are preferred, and the above-mentioned benzotrifluoride, perfluorohexane, and F-decanol are more preferably used. The content of the fluoro compound is preferably 0.01 to 20% by volume, more preferably 0.1 to 2% by volume, based on the total amount of the solvent. Further, the content of the fluorous solvent is preferably 0.01 to 30% by weight, more preferably 0.1 to 4% by weight in the total solvent.

  When the organic semiconductor layer is formed by mixing the electron-donating organic material having the structure represented by the general formula (1) or the general formula (2) and the electron-accepting organic material, the general formula (1) or the general formula Add the electron-donating organic material having the structure represented by (2) and the electron-accepting organic material to the solvent at a desired ratio, dissolve the solution using a method such as heating, stirring, or ultrasonic irradiation to make a solution, Apply on a transparent electrode. In this case, the photoelectric conversion efficiency of the photovoltaic element can be improved by using a mixture of two or more solvents. This is presumably because the electron-donating organic material and the electron-accepting organic material undergo phase separation at the nano level, and a carrier path that forms a path for electrons and holes is formed. As the solvent to be combined, an optimal combination type can be selected depending on the types of the electron donating organic material and the electron accepting organic material to be used. When the electron donating organic material having the structure represented by the general formula (1) or the general formula (2) is used, preferable solvents to be combined include chloroform and chlorobenzene among the above. In this case, the mixing volume ratio of each solvent is preferably in the range of chloroform: chlorobenzene = 5: 95 to 95: 5, more preferably in the range of chloroform: chlorobenzene = 10: 90 to 90:10. Further, when an organic semiconductor layer is formed by laminating an electron donating organic material and an electron accepting organic material having a structure represented by the general formula (1) or (2), for example, an electron donating organic material After forming a layer having an electron-donating organic material by applying the above solution, a layer of the electron-accepting organic material is applied to form a layer. Here, when the electron-donating organic material and the electron-accepting organic material are low molecular weight substances having a molecular weight of about 1000 or less, it is possible to form a layer using a vapor deposition method.

  For organic semiconductor layer formation, spin coating, blade coating, slit die coating, screen printing coating, bar coater coating, mold coating, printing transfer method, dip pulling method, ink jet method, spray method, vacuum deposition method, etc. This method may be used, and the formation method may be selected according to the characteristics of the organic semiconductor layer to be obtained, such as film thickness control and orientation control. For example, when spin coating is applied, the electron donating organic material having the structure represented by the general formula (1) or the general formula (2) and the electron accepting organic material have a concentration of 1 to 20 g / l (general It is represented by the general formula (1) or the general formula (2) with respect to the volume of the solution containing the electron-donating organic material having the structure represented by the formula (1) or the general formula (2), the electron-accepting organic material, and the solvent. The weight of the electron-donating organic material and the electron-accepting organic material having the above-described structure is preferable. By setting the concentration, a homogeneous organic semiconductor layer having a thickness of 5 to 200 nm can be easily obtained. In order to remove the solvent, the formed organic semiconductor layer may be subjected to an annealing treatment under reduced pressure or in an inert atmosphere (in a nitrogen or argon atmosphere). A preferable temperature for the annealing treatment is 40 ° C to 300 ° C, more preferably 50 ° C to 200 ° C. Further, by performing the annealing treatment, the effective area where the stacked layers permeate and contact each other at the interface increases, and the short-circuit current can be increased. This annealing treatment may be performed after the formation of the negative electrode.

  Next, a metal electrode such as Al (corresponding to a negative electrode in this case) is formed on the organic semiconductor layer by vacuum deposition or sputtering. When the metal electrode is vacuum-deposited using a low molecular organic material for the electron transport layer, it is preferable that the metal electrode is continuously formed while maintaining the vacuum.

  When a hole transport layer is provided between the positive electrode and the organic semiconductor layer, a desired p-type organic semiconductor material (such as PEDOT) is applied on the positive electrode by spin coating, bar coating, blade casting, or the like. Then, the solvent is removed using a vacuum thermostat or a hot plate to form a hole transport layer. In the case of using a low molecular organic material such as a phthalocyanine derivative or a porphyrin derivative, it is also possible to apply a vacuum vapor deposition method using a vacuum vapor deposition machine.

When an electron transport layer is provided between the organic semiconductor layer and the negative electrode, a desired n-type organic semiconductor material (such as fullerene derivatives) or an n-type inorganic semiconductor material (such as titanium oxide gel) is spin-coated on the organic semiconductor layer. After coating by a coating method, a casting method using a blade, a spray method, or the like, the solvent is removed using a vacuum thermostat or a hot plate to form an electron transport layer. When using a low molecular organic material such as a phenanthroline derivative or C _60, it is also possible to apply a vacuum deposition method using a vacuum deposition machine.

  The photovoltaic element of the present invention can be applied to various photoelectric conversion devices using a photoelectric conversion function, an optical rectification function, and the like. For example, it is useful for photovoltaic cells (such as solar cells), electronic elements (such as optical sensors, optical switches, and phototransistors), optical recording materials (such as optical memories), and the like.

Hereinafter, the present invention will be described more specifically based on examples. In addition, this invention is not limited to the following Example. Of the compounds used in the examples and the like, those using abbreviations are shown below.
ITO: indium tin oxide PEDOT: polyethylene dioxythiophene PSS: polystyrene sulfonate PC ₇₀ BM: phenyl C71 butyric acid methyl ester Eg: band gap HOMO: highest occupied molecular orbital Isc: short circuit current density Voc: open circuit voltage FF: fill Factor η: Photoelectric conversion efficiency For the ¹ H-NMR measurement, an FT-NMR apparatus (JEOL JNM-EX270 manufactured by JEOL Ltd.) was used. Moreover, the average molecular weight (number average molecular weight, weight average molecular weight) was calculated by an absolute calibration curve method using a GPC apparatus (manufactured by TOSOH Co., Ltd., to which chloroform was fed, high-speed GPC apparatus HLC-8220 GPC). The degree of polymerization n was calculated by the following formula.
Degree of polymerization n = [(weight average molecular weight) / (molecular weight of repeating unit)]
The light absorption edge wavelength is an ultraviolet-visible absorption spectrum (measurement wavelength) of a thin film formed on glass with a thickness of about 60 nm using a U-3010 spectrophotometer manufactured by Hitachi, Ltd. (Range: 300-900 nm). The band gap (Eg) was calculated from the light absorption edge wavelength by the following equation. The thin film was formed by spin coating using chloroform as a solvent.
Eg (eV) = 1240 / light absorption edge wavelength of thin film (nm)
In addition, the highest occupied molecular orbital (HOMO) level was determined by using a surface analyzer (in-air ultraviolet photoelectron spectrometer AC-1 type, manufactured by Riken Kikai Co., Ltd.) for a thin film formed on ITO glass to a thickness of about 60 nm. ). The thin film was formed by spin coating using chloroform as a solvent.

Synthesis example 1
Compound A-1 was synthesized by the method shown in Formula 1. Compound (1-h) in Synthesis Example 1 was synthesized with reference to the method described in Macromolecules 2004, 37, 8978-8983.

N-bromosuccinimide (Wako Pure Chemical Industries, Ltd.) was added to a mixed solution of 50.0 g (0.21 mol) of dimethylformamide (30 ml) and dichloromethane (90 ml) of 3-Iodoanisole (1-a) (manufactured by Wako Pure Chemical Industries, Ltd.). 39.2 g (0.22 mol) (made by Co., Ltd.) was added at room temperature, and it stirred at 60 degreeC for 6 hours. The reaction solution was cooled to room temperature, 50 ml of 1M aqueous sodium hydroxide solution was added, and the mixture was extracted twice with 120 ml of hexane. The organic layer was washed twice with 50 ml of 1M aqueous sodium hydroxide solution, 5 times with 100 ml of water and once with 100 ml of saturated brine, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by column chromatography (filler: silica gel, eluent: hexane) to obtain 59.2 g (yield 90%) of compound (1-b) as a colorless oil. The ¹ H-NMR measurement result of the compound (1-b) is shown.
¹ H-NMR (CDCl ₃ , ppm): 7.44 (d, J = 8.6 Hz, 1H), 7.37 (d, J = 2.0 Hz, 1H), 6.75 (dd, J = 8) .4 and 2.0 Hz, 1H), 3.75 (s, 3H).

  While stirring 31.2 g (100 mmol) of the above compound (1-b) and 100 ml of triethylamine (manufactured by Nacalai Tesque), 380 mg of copper iodide (manufactured by Wako Pure Chemical Industries, Ltd.), bis (tri 700 mg of phenylphosphine) palladium dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and then 17 ml (120 mmol) of trimethylsilylacetylene (manufactured by Aldrich) were added at room temperature and stirred for 4 hours. After completion of the stirring, the reaction mixture was filtered through Celite, and the solvent was distilled off under reduced pressure. The residue was passed through short column chromatography (filler: silica gel, eluent: hexane: ethyl acetate = 4: 1), and the solvent was distilled off under reduced pressure to obtain compound (1-c) as a yellow oil (31 g). The obtained compound (1-c) was used in the next reaction without further purification.

31 g of the above compound (1-c) was dissolved in a methanol / tetrahydrofuran mixed solvent (50 ml / 50 ml), and 1.4 g (10 mmol) of potassium carbonate was added to the stirring place, followed by stirring at room temperature for 12 hours. After stirring, 50 ml of 1M hydrochloric acid and 100 ml of ethyl acetate were added and stirred for 5 minutes, and then the organic layer was washed twice with saturated brine. The solvent was dried over anhydrous magnesium sulfate and evaporated under reduced pressure. Purification by column chromatography (filler: silica gel, eluent: hexane: ethyl acetate = 5: 1) gave compound (1-d) as a colorless oil (17.3 g, yield 90%). The ¹ H-NMR measurement result of the compound (1-d) is shown.
¹ H-NMR (CDCl ₃ , ppm): 7.44 (d, J = 8.9 Hz, 1H), 7.05 (d, J = 3.2 Hz, 1H), 6.78 (dd, J = 8) .9 and 3.4 Hz, 1H), 3.78 (s, 3H), 3.36 (s, 1H).

17.5 g (83 mmol) of the above compound (1-d) and 25.9 g (83 mmol) of (1-b) were dissolved in a diisopropylamine / toluene mixed solvent (12 ml / 36 ml), and copper iodide was added thereto while stirring. 340 mg (manufactured by Wako Pure Chemical Industries, Ltd.) and 700 mg of bis (triphenylphosphine) palladium dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at room temperature for 6 hours. After stirring, 100 ml of 1M hydrochloric acid was added, and extracted 3 times with 80 ml of methylene chloride. The solvent was dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was passed through short column chromatography (filler: silica gel, eluent: chloroform) and recrystallized from a mixed solvent of ethyl acetate / hexane to give compound (1-e) as a pale yellow solid (18.6 g, yield). 57%). The ¹ H-NMR measurement result of the compound (1-e) is shown.
¹ H-NMR (CDCl ₃ , ppm): 7.48 (d, J = 8.9 Hz, 2H), 7.13 (d, J = 2.9 Hz, 2H), 6.78 (dd, J = 8 .9 and 2.9 Hz, 2H), 3.81 (s, 6H).

3.8 g (9.5 mmol) of the above compound (1-e) was dissolved in 400 ml of diethyl ether and stirred at a concentration of 1.6 M n-butyllithium hexane solution (manufactured by Wako Pure Chemical Industries, Ltd.). 13 ml (20.8 mmol) was added dropwise at −78 ° C., and the mixture was stirred at −20 ° C. for 2 hours. After adding 6.1 ml (22 mmol) of dichlorohexylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) at −50 ° C., the mixture was stirred at −50 ° C. for 2 hours and further at room temperature for 2 hours. After adding 10 ml of ethanol and 5 ml of triethylamine (manufactured by Nacalai Tesque) at room temperature, the reaction solution was stirred at room temperature for 12 hours. After stirring, insolubles were filtered off in the solvent, and the solvent was distilled off under reduced pressure. Purification by column chromatography (filler: silica gel, eluent: hexane: ethyl acetate = 20: 1) gave compound (1-f) as a colorless oil (8.0 g, yield 58%). The ¹ H-NMR measurement result of the compound (1-f) is shown.
¹ H-NMR (CDCl ₃ , ppm): 7.56 (d, J = 8.1 Hz, 2H), 7.13 (d, J = 2.4 Hz, 2H), 6.89 (dd, J = 8) .1 and 2.4 Hz, 2H), 3.83 (s, 6H), 1.2-0.6 (m, 62H).

While stirring 50 ml of dry tetrahydrofuran, 310 mg of granular lithium (manufactured by Aldrich) and then 5.72 g (45 mmol) of naphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature for 4 hours. To the prepared lithium naphthalene solution, 50 ml of a tetrahydrofuran solution of 8.0 g (11 mmol) of the above compound (1-f) was added at room temperature, followed by stirring at room temperature for 5 minutes. Then, 25 ml of a tetrahydrofuran solution containing 11.3 g of iodine (manufactured by Wako Pure Chemical Industries, Ltd.) (45 mmol) was added and stirred for 30 minutes. After adding 100 ml of saturated aqueous sodium thiosulfate solution, 80 ml of diethyl ether was added, and the organic layer was washed twice with 100 ml of saturated brine. The solvent was dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography (filler: silica gel, eluent: hexane: methylene chloride = 4: 1) to obtain compound (1-g) as a pale yellow oil (3.3 g, yield 23%). . The ¹ H-NMR measurement result of the compound (1-g) is shown.
¹ H-NMR (CDCl ₃ , ppm): 7.44 (d, J = 7.6 Hz, 2H), 6.85 (d, J = 2.2 Hz, 2H), 6.72 (dd, J = 7 .6 and 2.2 Hz, 2H), 3.85 (s, 6H), 1.3-0.6 (m, 52H).

In a place where 2.2 g (3.47 mmol) of the above compound (1-g) was dissolved in 60 ml of tetrahydrofuran and stirred at −78 ° C., a 1.0 M secondary butyl lithium cyclohexane / hexane solution (manufactured by Kanto Chemical Co., Inc.) ) 14 ml (14 mmol) was added dropwise at -78 ° C. After stirring the reaction solution at −50 ° C. for 2 hours, 3.2 g (17 of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (manufactured by Tokyo Chemical Industry Co., Ltd.)) .4 mmol) was added at −78 ° C., and the reaction solution was stirred at room temperature for 8 hours. After completion of the stirring, 80 ml of diethyl ether was added, and the organic layer was washed 5 times with 80 ml of water and once with 80 ml of saturated saline. The solvent was dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was recrystallized from ethanol to obtain compound (1-h) (500 mg, yield 18%) as light yellow crystals. The ¹ H-NMR measurement result of the compound (1-h) is shown.
¹ H-NMR (CDCl ₃ , ppm): 7.81 (s, 2H), 6.83 (s, 2H), 3.88 (s, 6H), 1.42-0.93 (m, 40H) 1.37 (s, 24H), 0.79 (t, J = 6.6 Hz, 12H).

  To 1,600 ml of 48% hydrobromic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 30.0 g (0.22 mol) of 2,1,3-benzothiazole (1-i) was added and bromine was stirred at room temperature. 70.4 g (0.44 mmol) was added dropwise. After completion of dropping, the reaction solution was stirred at 100 ° C. for 8 hours. The reaction mixture was cooled to room temperature, 500 ml of water was added, the precipitated solid was collected by filtration, and washed with water and then ethanol. The crude product was refluxed in 500 ml of ethanol for 1 hour, and after cooling to room temperature, the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure to obtain compound (1-j) as a pale yellow solid (50.4 g, yield 78%).

After bubbling 400 ml of a toluene solution of compound (1-j) 8.0 g (27 mmol) and 2-tributyltinthiophene 24.4 g (Aldrich) (66 mmol) with nitrogen, dichlorobis (triphenylphosphine) palladium catalyst (Tokyo Chemical Industry ( 600 mg) was added and refluxed for 8 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. 200 ml of ethanol was added to the residue and stirred at room temperature for 30 minutes. After the precipitate was collected by filtration, the solid was washed with ethanol and then with hexane. The obtained crude product was recrystallized from chloroform to obtain the compound (1-k) as an orange solid (4.6 g, yield 56%). The measurement result of ¹ H-NMR of the compound (1-k) is shown below.
¹ H-NMR (CDCl ₃ , ppm): 8.08 (dd, J = 3.9 and 1.1 Hz, 2H), 7.80 (s, 1H), 7.43 (dd, J = 4.9) and 1.1 Hz, 2H), 7.52 (dd, J = 4.9 and 3.9 Hz, 2H).

To 80 ml of a DMF solution of 1.2 g (4.0 mmol) of the above compound (1-k), 1.57 g (8.8 mmol) of N-bromosuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred for 1 hour at room temperature. . After completion of the reaction, the precipitated solid was collected by filtration and then washed with DMF and then with acetone. Recrystallization from chloroform gave the compound (1-1) as an orange solid (820 mg, yield 64%). The measurement result of ¹ H-NMR of the compound (1-l) is shown below.
¹ H-NMR (CDCl ₃ , ppm): 8.08 (d, J = 4.3 Hz, 2H), 7.77 (s, 2H), 7.14 (d, J = 4.3 Hz, 2H).

  When 89 mg (0.10 mmol) of the above compound (1-l) and 46 mg (0.10 mmol) of the compound (1-h) were dissolved in 5 ml of toluene, 1 ml of 1M potassium carbonate aqueous solution, Alquat 336 (manufactured by Aldrich) 1 Drops and 11 mg of tetrakis (triphenylphosphine) palladium catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 100 ° C. for 8 hours under a nitrogen atmosphere. Next, 30 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C. for 1 hour. Subsequently, phenylboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd. 50 mg) was added, and the mixture was further stirred at 100 ° C. for 1 hour. After completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was collected by filtration and washed with methanol, water, and acetone in this order. The obtained solid was refluxed in 80 ml of acetone for 1 hour and filtered to remove acetone-soluble matter. Next, the crude product was dissolved in 80 ml of chloroform, 30 mg of catalyst removal polymer QuadraSilMP (manufactured by Aldrich) was added, and the mixture was refluxed for 1 hour. After the chloroform solution was filtered through Celite (manufactured by Nacalai Tesque), the solvent was distilled off under reduced pressure. The obtained solid was again dissolved in chloroform, passed through a silica gel column (eluent: chloroform), concentrated, and reprecipitated in methanol to obtain compound A-1 (31 mg). The weight average molecular weight was 17,200, the number average molecular weight was 10,100, and the degree of polymerization n was 18.5. The light absorption edge wavelength was 663 nm, the band gap (Eg) was 1.87 eV, and the highest occupied molecular orbital (HOMO) level was −5.36 eV.

Synthesis example 2
Compound A-2 was synthesized by the method shown in Formula 2.

  When 20.0 g (68 mmol) of the above compound (1-j) is suspended in 750 ml of ethanol and stirred using a mechanical stirrer, 37.8 g (1 mol) of sodium tetrahydroborate is divided into 5 times. Added at 0 ° C. over time. The reaction solution mixture was stirred at 0 ° C. for 5 hours and then allowed to stand at room temperature for 12 hours. Ethanol was distilled off under reduced pressure to approximately 250 ml, and then 100 ml of water was slowly added at 0 ° C. After adding 200 ml of chloroform, solids insoluble in the aqueous layer and the organic layer were separated by filtration. The aqueous layer was extracted 3 times with 100 ml of chloroform, and the collected organic layer was dried over magnesium sulfate. Chloroform was distilled off under reduced pressure to obtain compound (2-a) as a pale orange solid (10.2 g, yield 56%). Compound (2-a) was used in the following reaction without further purification.

One drop of concentrated sulfuric acid was added to 120 ml of chloroform solution of 4.0 g (15 mmol) of the above compound (2-a) and 3.16 g (15 mmol) of benzyl (Tokyo Chemical Industry Co., Ltd.) at room temperature, and the reaction solution was refluxed for 5 hours. did. The reaction solution was cooled to room temperature, 50 ml of 5% aqueous sodium carbonate solution was added, and the organic layer was dried with 100 ml of water and then with 100 ml of saturated brine. The solvent was dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The crude product was washed with methanol to obtain compound (2-b) as a pale yellow solid (5.2 g, yield 79%). The measurement result of ¹ H-NMR of the compound (2-b) is shown below.
¹ H-NMR (CDCl ₃ , ppm): 7.91 (s, 2H), 7.65 (m, 4H), 7.38 (m, 6H).

80 ml of a toluene solution of 4.4 g (10.0 mmol) of compound (2-b) and 11.2 g (30 mmol) of 2-tributyltinthiophene (Aldrich) was bubbled with nitrogen, and then dichlorobis (triphenylphosphine) palladium catalyst (Tokyo) 350 mg of Kasei Kogyo Co., Ltd.) was added and refluxed for 8 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. 200 ml of ethanol was added to the residue and stirred at room temperature for 30 minutes. After the precipitate was collected by filtration, the solid was washed with ethanol and then with hexane. The obtained crude product was recrystallized from chloroform to obtain the compound (2-c) as a yellow solid (3.0 g, yield 34%). The measurement result of ¹ H-NMR of the compound (2-c) is shown below.
¹ H-NMR (CDCl ₃ , ppm): 8.15 (s, 2H), 7.88 (d, J = 4.1 Hz, 2H), 7.76-7.73 (m, 4H), 7. 52 (d, J = 4.9 Hz, 2H), 7.40-7.36 (m, 6H), 7.20-7.17 (m, 2H).

To 100 ml of a chloroform solution of 2.0 g (4.47 mmol) of the above compound (2-c) was added 1.75 g of N-bromosuccinimide (9.85 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred for 1 hour at room temperature. After completion of the reaction, 50 ml of 5% aqueous sodium thiosulfate solution was added and stirred for 10 minutes. The organic layer was washed once with 100 ml of water and then with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The crude product was passed through a silica gel column (eluent: chloroform), and then the solid was washed with acetone to obtain compound (2-d) as an orange solid (1.16 g, yield 43%). The measurement result of ¹ H-NMR of the compound (2-d) is shown below.
¹ H-NMR (CDCl ₃ , ppm): 8.07 (s, 2H), 7.71-7.68 (m, 4H), 7.57 (d, J = 4.1 Hz, 2H), 7. 44-7.37 (m, 6H), 7.12 (d, J = 4.1 Hz, 2H).

  When 89 mg (0.10 mmol) of the above compound (2-d) and 60 mg (0.10 mmol) of the compound (1-h) were dissolved in 5 ml of toluene, 1 ml of 1M potassium carbonate aqueous solution, Alquat 336 (manufactured by Aldrich) 1 Drops and 11 mg of tetrakis (triphenylphosphine) palladium catalyst (Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 100 ° C. for 8 hours under a nitrogen atmosphere. Next, 30 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C. for 1 hour. Next, 50 mg of phenylboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C. for 1 hour. After completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was collected by filtration and washed with methanol, water, and acetone in this order. The obtained solid was refluxed in 80 ml of acetone for 1 hour and filtered to remove acetone-soluble matter. Next, the crude product was dissolved in 80 ml of chloroform, 30 mg of a catalyst-removed polymer QuadraSilMP (manufactured by Aldrich) was added, and the mixture was refluxed for 1 hour. After the chloroform solution was filtered through Celite (manufactured by Nacalai Tesque), the solvent was distilled off under reduced pressure. The obtained solid was again dissolved in chloroform, passed through a silica gel column (eluent: chloroform), concentrated, and reprecipitated in methanol to obtain compound A-2 (11 mg). The weight average molecular weight was 23,600, the number average molecular weight was 14,400, and the degree of polymerization n was 21.9. The light absorption edge wavelength was 660 nm, the band gap (Eg) was 1.88 eV, and the highest occupied molecular orbital (HOMO) level was −5.26 eV.

Synthesis example 3
Compound A-3 was synthesized by the method shown in Formula 3.

  Compound (3-a) 10.2 g (52 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 ml of DMF, N-bromosuccinimide (Wako Pure Chemical Industries, Ltd.) 9.24 g (52 mmol) was added, and room temperature was added. For 3 hours. 200 ml of water and 200 ml of hexane were added to the reaction solution, and the organic layer was separated, washed with 200 ml of water, and then dried over anhydrous magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, free liquid: hexane) to obtain compound (3-b) as a colorless oil (14.4 g, yield 74%).

  When 20.0 g (72.7 mmol) of the above compound (3-b) was dissolved in 300 ml of tetrahydrofuran and cooled to −78 ° C., an n-butyllithium hexane solution having a concentration of 1.6 M (Wako Pure Chemical Industries, Ltd.) was obtained. 50 ml) was added dropwise. The reaction solution was stirred at −50 ° C. for 30 minutes and then cooled again to −78 ° C., and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Tokyo Chemical Industry Co., Ltd.). 17.6 g (94.5 mmol) was added. The reaction solution was further stirred at room temperature for 4 hours, and then 100 ml of water and 250 ml of ethyl acetate were added. The organic layer was washed 3 times with 100 ml of water and once with 100 ml of saturated brine, and then dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by column chromatography (filler: silica gel, eluent: hexane: dichloromethane = 1: 1) gave compound (3-c) as a colorless oil (16.5 g, yield 70%).

150 ml of DMF solution of 11.34 g (35.2 mmol) of the above compound (3-c) and 4.75 g (14.7 mmol) of 5,5′-dibromo-2,2′-bithiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.5 g (58.8 mmol) of potassium phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) and then 800 mg of bis (diphenylphosphinoferrocene) palladium dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added at 90 ° C. Stir for hours. After completion of the reaction, 200 ml of ethyl acetate and then 100 ml of water were added. The organic layer was washed 5 times with 200 ml of water and once with 100 ml of saturated brine, and then dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by column chromatography (filler: silica gel, eluent: hexane) gave compound (3-d) as a yellow oil (4.6 g, yield 56%). The measurement result of ¹ H-NMR of the compound (3-d) is shown below.

¹ H-NMR (CDCl ₃ , ppm): 7.16 (d, J = 5.2 Hz, 2H), 7.11 (d, J = 3.6 Hz, 2H), 6.93 (d, J = 5 .2 Hz, 2H), 2.78 (t, J = 7.0 Hz, 4H), 1.79-1.59 (m, 4H), 1.42-1.27 (m, 20H), 0.87 (T, J = 6.8 Hz, 6H).

When 3.68 g (6.61 mmol) of the compound (3-d) was dissolved in 50 ml of tetrahydrofuran and cooled to −78 ° C., an n-butyllithium hexane solution having a concentration of 1.6 M (Wako Pure Chemical Industries, Ltd.) (Made) 4.5 ml was dripped. The reaction solution was stirred at −50 ° C. for 30 minutes and then cooled again to −78 ° C., and 1.7 g (9.3 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained. , Tokyo Chemical Industry Co., Ltd.) was added. The reaction solution was further stirred at room temperature for 4 hours, and then 50 ml of water and then 100 ml of ethyl acetate were added. The organic layer was washed 3 times with 100 ml of water and once with 100 ml of saturated brine, and then dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by column chromatography (filler: silica gel, eluent: hexane) gave compound (3-e) as a brown oil (2.2 g, yield 49%). The measurement result of ¹ H-NMR of the compound (3-e) is shown below.

¹ H-NMR (CDCl ₃ , ppm): 7.46 (s, 1H), 7.17 (d, J = 5.0 Hz, 1H), 7.12 (d, J = 4.1 Hz, 2H), 7.08 (d, J = 4.1 Hz, 1H), 7.02 (d, J = 4.1 Hz, 1H), 6.93 (d, J = 5.0 Hz, 2H), 2.79 (t , J = 7.0 Hz, 2H), 2.78 (t, J = 7.0 Hz, 2H), 1.67-1.56 (m, 4H), 1.35 (s, 12H), 1.35. -1.26 (m, 20H), 0.88-0.85 (m, 6H).

To 15 ml of a DMF solution of 1.8 g (2.64 mmol) of the compound (3-e) and 3.50 mg (1.2 mmol) of the compound (1-j), potassium phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) 5 g (7.0 mmol) and then 100 mg of bis (diphenylphosphinoferrocene) palladium dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 90 ° C. for 8 hours. After completion of the reaction, 50 ml of chloroform and then 50 ml of water were added. The organic layer was washed 5 times with 50 ml of water and once with 50 ml of saturated brine, and then dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by column chromatography (filler: silica gel, eluent: hexane: dichloromethane = 5: 2) gave compound (3-f) as a black solid (1.25 g, yield 84%). The measurement result of ¹ H-NMR of the compound (3-f) is shown below.
¹ H-NMR (CDCl ₃ , ppm): 7.93 (s, 2H), 7.72 (s, 2H), 7.18 (d, J = 4.9 Hz, 2H), 7.13-7. 10 (m, 6H), 7.01 (d, J = 3.5 Hz, 2H), 6.94 (d, J = 4.9 Hz, 2H), 6.94 (d, J = 4.9 Hz, 2H) ), 2.86-2.75 (m, 8H), 1.76-1.60 (m, 8H), 1.5-1.2 (m, 40H), 0.88 (t, J = 6) .5Hz, 12H).

1.12 g (0.9 mmol) of the above compound (3-f) was dissolved in 50 ml of chloroform, and 320 mg of N-bromosuccinimide (1.8 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the stirring place. Stir at room temperature for 6 hours. After adding 100 ml of water to the reaction solution, the organic layer was washed twice with 100 ml of water and dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by column chromatography (filler: silica gel, free liquid: chloroform) to obtain the compound (3-g) as a black solid (1.08 g, yield 86%). The measurement result of ¹ H-NMR of the compound (3-g) is shown below.

¹ H-NMR (CDCl ₃ , ppm): 7.97 (s, 2H), 7.80 (s, 2H), 7.15 (s, 4H), 7.12 (d, J = 3.8 Hz, 2H), 6.97 (d, J = 3.8 Hz, 2H), 6.89 (s, 2H), 2.86 (t, J = 7.8 Hz, 4H), 2.72 (t, J = 4.9 Hz, 2H), 7.93 (s, 2H), 7.72 (s, 2H), 7.18 (d, J = 7.8 Hz, 4H), 1.82-1.57 (m, 8H), 1.43-1.29 (m, 40H), 0.88 (t, J = 6.8 Hz, 12H).

  When 80 mg (0.057 mmol) of the compound (3-g) and 51 mg (0.057 mmol) of the compound (1-h) were dissolved in 5 ml of toluene, 1 ml of a 1M aqueous potassium carbonate solution, Alquat 336 (manufactured by Aldrich) 1 Drops and 11 mg of tetrakis (triphenylphosphine) palladium catalyst (Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 100 ° C. for 8 hours under a nitrogen atmosphere. Next, 30 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C. for 1 hour. Next, 50 mg of phenylboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C. for 1 hour. After completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was collected by filtration and washed with methanol, water, and acetone in this order. The obtained solid was refluxed in 80 ml of acetone for 1 hour and filtered to remove acetone-soluble matter. Next, the crude product was dissolved in 80 ml of chloroform, 30 mg of a catalyst-removed polymer QuadraSilMP (manufactured by Aldrich) was added, and the mixture was refluxed for 1 hour. After the chloroform solution was filtered through Celite (manufactured by Nacalai Tesque), the solvent was distilled off under reduced pressure. The obtained solid was again dissolved in chloroform, passed through a silica gel column (eluent: chloroform), concentrated, and reprecipitated in methanol to obtain compound A-3 (32 mg). The weight average molecular weight was 81,100, the number average molecular weight was 21,500, and the degree of polymerization n was 43.3. The light absorption edge wavelength was 717 nm, the band gap (Eg) was 1.73 eV, and the highest occupied molecular orbital (HOMO) level was -5.22 eV.

Synthesis example 4
Compound B-1 was synthesized by the method shown in Formula 4.

  15 g of the above compound (3-b) was dissolved in 100 mL of diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) and cooled to -78 ° C. After adding 35 mL of n-butyllithium 1.6M hexane solution (made by Wako Pure Chemical Industries Ltd.), it heated up to -60 degreeC and added 6.2 mL of dimethylformamide (made by Kishida Chemical Co., Ltd.). The mixture was warmed to room temperature and stirred for 2 hours under a nitrogen atmosphere. 200 mL of 1N ammonium chloride aqueous solution and 100 mL of dichloromethane were added to the resulting solution, and the organic layer was separated, washed with 100 mL of water, and dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: dichloromethane) to obtain 12.1 g of compound (4-a).

  8.47 g of zinc powder (Wako Pure Chemical Industries, Ltd.) is added to 200 mL of tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) 200 mL, and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) 7.1 mL at 0 ° C. And 12.1 g of the compound (4-a) were added. After heating under reflux for 1 hour under a nitrogen atmosphere, the resulting solution was added to 1500 mL of ice water and 300 mL of dichloromethane was added. The organic layer was separated, washed with 100 mL of water, and dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: hexane) to obtain 7.47 g of compound (4-b).

  7.47 g of the above compound (4-b) was dissolved in 100 mL of dimethylformamide (manufactured by Kishida Chemical Co., Ltd.), 7.0 g of N-bromosuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and under a nitrogen atmosphere, Stir at room temperature for 4 hours. Water (100 mL), n-hexane (100 mL), and dichloromethane (100 mL) were added to the resulting solution, and the organic layer was separated, washed with water (100 mL), and dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: hexane) to obtain 6.94 g of compound (4-c).

  5.4 g of the above compound (4-c) was dissolved in 70 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and cooled to -78 ° C. After adding 15.0 mL of n-butyllithium 1.6M hexane solution (manufactured by Wako Pure Chemical Industries, Ltd.), the temperature was raised to −60 ° C., and 2-isopropoxy-4,4,5,5-tetramethyl was added. 3.4 g of -1,3,2-dioxaborolane (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The mixture was warmed to room temperature and stirred for 24 hours under a nitrogen atmosphere. 100 mL of water and 100 mL of dichloromethane were added to the resulting solution, and the organic layer was separated, washed with 100 mL of water, and dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: dichloromethane / hexane) to obtain 2.36 g of compound (4-d).

  0.17 g of the compound (1-j) and 0.355 g of the compound (4-d) were dissolved in 20 mL of toluene. 7 mg of bis (dibenzylideneacetone) dipalladium (manufactured by Aldrich), 6 mg of tri (t-butyl) phosphine (manufactured by Aldrich), and 0.22 g of t-butoxy sodium (manufactured by Wako Pure Chemical Industries, Ltd.) were added. The mixture was stirred at 100 ° C. for 20 hours under a nitrogen atmosphere. Bromobenzene (Tokyo Chemical Industry Co., Ltd.) 0.16g was added, and it stirred at 100 degreeC continuously for 5 hours. From the obtained suspension, the solvent was distilled off under reduced pressure using a rotary evaporator and washed with hot methanol and hot hexane. The obtained solid was dissolved in chloroform and purified by column chromatography (filler: silica gel, eluent: chloroform) to obtain 52 mg of compound B-1. The weight average molecular weight was 3,600, the number average molecular weight was 2,900, and the degree of polymerization n was 7.3. The light absorption edge wavelength was 775 nm, the band gap (Eg) was 1.60 eV, and the highest occupied molecular orbital (HOMO) level was -4.92.

Synthesis example 5
Compound B-2 was synthesized by the method shown in Formula 5.

  0.15 g of the compound (1-l) and 0.20 g of the compound (4-d) were dissolved in 20 mL of toluene. 7 mg of bis (dibenzylideneacetone) dipalladium (manufactured by Aldrich), 6 mg of tri (t-butyl) phosphine (manufactured by Aldrich), and 0.22 g of t-butoxy sodium (manufactured by Wako Pure Chemical Industries, Ltd.) were added. The mixture was stirred at 100 ° C. for 20 hours under a nitrogen atmosphere. Bromobenzene (Tokyo Chemical Industry Co., Ltd.) 0.16g was added, and it stirred at 100 degreeC continuously for 5 hours. From the obtained suspension, the solvent was distilled off under reduced pressure using a rotary evaporator and washed with hot methanol and hot hexane. The obtained solid was dissolved in chloroform and purified by column chromatography (filler: silica gel, eluent: chloroform) to obtain 48 mg of compound B-2. The weight average molecular weight was 4,400, the number average molecular weight was 3,100, and the degree of polymerization n was 6.7. The light absorption edge wavelength was 755 nm, the band gap (Eg) was 1.64 eV, and the highest occupied molecular orbital (HOMO) level was −4.88.

Synthesis Example 6
Compound B-3 was synthesized by the method shown in Formula 6.

  1,3-dibromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.34 g, bis (pinacolato) diboron (manufactured by BASF) 0.85 g, potassium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.86 g In addition to 7 ml of 1,4-dioxane (manufactured by Wako Pure Chemical Industries, Ltd.), 0.21 g of [bis (diphenylphosphino) ferrocene] dichloropalladium (manufactured by Aldrich) was added, followed by stirring at 80 ° C. for 9 hours. 100 ml of water and 100 ml of ethyl acetate were added to the resulting solution, and the organic layer was separated, washed with 100 ml of water and then dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by column chromatography (filler: silica gel, free liquid: dichloromethane) to obtain compound (6-a).

  17 mg of the compound (6-a) and 110 mg of the compound (3-g) were dissolved in 6 ml of toluene. 2 ml of water, 0.22 g of potassium carbonate, 9 mg of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1 drop of Alquat 336 (manufactured by Aldrich) were added thereto, and the mixture was stirred at 100 ° C. for 12 hours under a nitrogen atmosphere. did. Subsequently, 40 mg of phenylboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred for 2 hours. 50 ml of methanol was added to the obtained solution, and the precipitated solid was collected by filtration and washed with methanol, water and acetone in this order. The obtained solid was dissolved in chloroform, passed through a silica gel column (eluent: chloroform), and then reprecipitated from methanol to obtain 65 mg of compound (B-3). The weight average molecular weight was 8,700, the number average molecular weight was 5,700, and the degree of polymerization n was 6.5. The light absorption edge wavelength was 720 nm, the band gap (Eg) was 1.72 eV, and the highest occupied molecular orbital (HOMO) level was -5.03.

Synthesis example 7
Compound B-4 was synthesized by the method shown in Formula 7.

  Compound (7-a) was synthesized by the method described in Macromolecules 2008, 41, 7296-7305.

  When 46 mg (0.1 mmol) of the compound (7-a) and 91 mg (0.1 mmol) of the compound (1-l) were dissolved in 5 ml of toluene, 1 ml of 1M potassium carbonate aqueous solution, Alquat 336 (manufactured by Aldrich) 1 Drops and 11 mg of tetrakis (triphenylphosphine) palladium catalyst (Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 100 ° C. for 8 hours under a nitrogen atmosphere. Next, 30 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C. for 1 hour. Next, 50 mg of phenylboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C. for 1 hour. After completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was collected by filtration and washed with methanol, water, and acetone in this order. The obtained solid was refluxed in 80 ml of acetone for 1 hour and filtered to remove acetone-soluble matter. Next, the crude product was dissolved in 80 ml of chloroform, 30 mg of a catalyst-removed polymer QuadraSilMP (manufactured by Aldrich) was added, and the mixture was refluxed for 1 hour. After the chloroform solution was filtered through Celite (manufactured by Nacalai Tesque), the solvent was distilled off under reduced pressure. The obtained solid was dissolved again in chloroform, passed through a silica gel column (eluent: chloroform), concentrated, and reprecipitated in methanol to obtain Compound B-4 (56 mg). The weight average molecular weight was 16,700, the number average molecular weight was 11,200, and the degree of polymerization n was 17.6. The light absorption edge wavelength was 670 nm, the band gap (Eg) was 1.85 eV, and the highest occupied molecular orbital (HOMO) level was −5.33.

  Various physical properties of the compounds A-1 to A-3 and the compounds B-1 to B-4 (weight average molecular weight, number average molecular weight, light absorption edge wavelength, band gap (Eg), highest occupied molecular orbital (HOMO) quasi Are summarized in Table 1.

Example 1
A-1 (1 mg) and PC ₇₀ BM (4 mg, manufactured by Solenne) are added to a sample bottle containing 0.25 ml of chlorobenzene, and an ultrasonic cleaning machine (US-2 manufactured by Inoue Seieido Co., Ltd.) Name), and output 120W) for 30 minutes to obtain a solution A.

A glass substrate on which an ITO transparent conductive layer serving as a positive electrode having a thickness of 120 nm was deposited by sputtering was cut into 38 mm × 46 mm, and then ITO was patterned into a 38 mm × 13 mm rectangular shape by photolithography. The obtained substrate was subjected to ultrasonic cleaning for 10 minutes with an alkali cleaning solution (“Semico Clean” EL56 (trade name), manufactured by Furuuchi Chemical Co., Ltd.), and then washed with ultrapure water. After this substrate was UV / ozone treated for 30 minutes, a PEDOT: PSS aqueous solution (0.8% by weight of PEDOT, 0.5% by weight of PPS) serving as a hole transport layer was formed on the substrate to a thickness of 60 nm by spin coating. did. After heating and drying at 200 ° C. for 5 minutes using a hot plate, the above solution A was dropped onto the PEDOT: PSS layer, and an organic semiconductor layer having a thickness of 100 nm was formed by spin coating. Thereafter, the substrate on which the organic semiconductor layer is formed and the cathode mask are placed in a vacuum evaporation apparatus, and the vacuum is exhausted again until the degree of vacuum in the apparatus becomes 1 × 10 ⁻³ Pa or less. An aluminum layer was deposited to a thickness of 80 nm. As described above, a photovoltaic device having an area where the stripe-shaped ITO layer intersects with the aluminum layer was 5 mm × 5 mm was produced.

The positive and negative electrodes of the photovoltaic device thus fabricated were connected to a picoammeter / voltage source 4140B manufactured by Hewlett-Packard Co., and simulated sunlight (from Yamashita Denso Co., Ltd., simplified) from the ITO layer side in the atmosphere. Type solar simulator YSS-E40, spectrum shape: AM1.5, intensity: 100 mW / cm ² ), and the current value was measured when the applied voltage was changed from −1V to + 2V. At this time, the short-circuit current density (value of the current density when the applied voltage is 0 V) is 8.36 mA / cm ² , the open circuit voltage (value of the applied voltage when the current density is 0) is 0.92 V, and the fill factor (FF) was 0.46, and the photoelectric conversion efficiency calculated from these values was 3.55%. The fill factor and photoelectric conversion efficiency were calculated by the following equations.
Fill factor = IVmax (mA · V / cm ² ) / (Short-circuit current density (mA / cm ² ) × Open circuit voltage (V))
(Here, IVmax is the value of the product of the current density and the applied voltage at the point where the product of the current density and the applied voltage becomes maximum when the applied voltage is between 0 V and the open circuit voltage value.)
Photoelectric conversion efficiency = [(short circuit current density (mA / cm ² ) × open voltage (V) × fill factor) / pseudo sunlight intensity (100 mW / cm ² )] × 100 (%)
The fill factor and photoelectric conversion efficiency in the following examples and comparative examples were all calculated by the above formula.

Example 2
A photovoltaic device was produced in the same manner as in Example 1 except that A-2 was used in place of A-1, and current-voltage characteristics were measured. At this time, the short-circuit current density was 8.72 mA / cm ² , the open-circuit voltage was 0.84 V, the fill factor (FF) was 0.48, and the photoelectric conversion efficiency calculated from these values was 3.49%. .

Example 3
A photovoltaic device was produced in the same manner as in Example 1 except that A-3 was used instead of A-1, and current-voltage characteristics were measured. At this time, the short-circuit current density was 8.28 mA / cm ² , the open-circuit voltage was 0.84 V, the fill factor (FF) was 0.46, and the photoelectric conversion efficiency calculated from these values was 3.17%. .

Comparative Example 1
A photovoltaic device was produced in the same manner as in Example 1 except that B-1 was used instead of A-1, and current-voltage characteristics were measured. The short-circuit current density at this time was 4.90 mA / cm ² , the open circuit voltage was 0.64 V, and the fill factor (FF) was 0.34. The photoelectric conversion efficiency calculated from these values was 1.09%. .

Comparative Example 2
A photovoltaic device was produced in the same manner as in Example 1 except that B-2 was used instead of A-1, and current-voltage characteristics were measured. The short-circuit current density at this time was 5.21 mA / cm ² , the open-circuit voltage was 0.60 V, the fill factor (FF) was 0.34, and the photoelectric conversion efficiency calculated from these values was 1.05%. .

Comparative Example 3
A photovoltaic device was produced in the same manner as in Example 1 except that B-3 was used in place of A-1, and current-voltage characteristics were measured. At this time, the short-circuit current density was 6.12 mA / cm ² , the open-circuit voltage was 0.81 V, the fill factor (FF) was 0.35, and the photoelectric conversion efficiency calculated from these values was 1.72%. .

Comparative Example 4
A photovoltaic device was produced in the same manner as in Example 1 except that B-4 was used instead of A-1, and current-voltage characteristics were measured. The short-circuit current density at this time was 7.56 mA / cm ² , the open circuit voltage was 0.74 V, the fill factor (FF) was 0.45, and the photoelectric conversion efficiency calculated from these values was 2.52%. .

Comparative Example 5
A photovoltaic device was produced in the same manner as in Example 1 except that the compound (1-g) described in Synthesis Example 1 was used instead of A-1, and current-voltage characteristics were measured. The short-circuit current density at this time was 0.12 mA / cm ² , the open-circuit voltage was 0.09 V, the fill factor (FF) was 0.10, and the photoelectric conversion efficiency calculated from these values was 0.001%. .

  The results of Examples 1 to 3 and Comparative Examples 1 to 5 are summarized in Table 2.

  As is clear from Table 2, the photovoltaic elements (Examples 1 to 3) produced using the electron donating organic material having the structure represented by the general formula (1) or the general formula (2) are the same. High photoelectric conversion efficiency was shown compared with the other photovoltaic device (Comparative Examples 1-5) produced on condition of this.

DESCRIPTION OF SYMBOLS 1 Board | substrate 2 Positive electrode 3 Organic-semiconductor layer 4 Negative electrode 5 Layer which has an electron-donating organic material which has a structure represented by General formula (1) or General formula (2) 6 Layer which has electron-accepting organic material

Claims (8)

A photovoltaic device material comprising an electron-donating organic material having a structure represented by the general formula (1) or (2).

(In the general formula (1), X ¹ and X ² may be the same or different and represent silicon, phosphorus or nitrogen. R ^{1 to} R ⁴ in the general formula (1), the general formula (2 R ¹ and R ³ may be the same or different and are selected from hydrogen, alkyl group, alkoxy group, aryl group, heteroaryl group and halogen, provided that X ¹ and X ² are trivalent for phosphorus or nitrogen, R ² and R ⁴ are absent. in formula (1) to (2), ring B, and ring C and ring D are aryl or heteroaryl ring which may be substituted A represents a single bond or a divalent linking group, m represents a range of 0 to 10, and n represents a range of 2 to 1,000. The material for a photovoltaic device according to claim 1, wherein A in the general formula (1) or (2) includes a condensed heteroarylene structure having a nitrogen-containing double bond. The material for a photovoltaic device according to claim 1 or 2, wherein in formula (1) or (2), ring B, ring C, and ring D are optionally substituted benzene rings. The photovoltaic element material according to claim ^1, wherein X ¹ and X ² in the general formula (1) are silicon. Furthermore, the material for photovoltaic elements in any one of Claims 1-4 containing an electron-accepting organic material. The photovoltaic element material according to claim 5, wherein the electron-accepting organic material is a fullerene compound. The photovoltaic element material according to claim 6, wherein the fullerene compound is a C ₇₀ derivative. A photovoltaic element having at least a positive electrode and a negative electrode, wherein the photovoltaic element comprises the photovoltaic element material according to any one of claims 1 to 7 between the negative electrode and the positive electrode.

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