JP2012167241A - New copolymer, organic semiconductor material, and organic electronic device, photoelectric conversion element and solar cell module each using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new copolymer with high solubility and having absorption in a long wavelength region, that is suitable for a photoelectric conversion element.SOLUTION: This copolymer is expressed by general formula (1), and has a weight-average molecular weight in terms of polystyrene of 2×10-1×10, where in the formula, Rrepresents a (substituted) alkyl group, (substituted) alkenyl group or (substituted) aryl group; Rto Reach independently represents a hydrogen atom, a halogen atom, a (substituted) alkyl group, (substituted) alkenyl group or (substituted) aryl group.

Description

  The present invention relates to a novel copolymer having a repeating unit having a specific skeleton, an organic semiconductor material containing the same, an organic electronic device using the same, and a solar cell module.

As semiconductor materials for devices such as organic EL, organic thin-film transistors, and organic light-emitting sensors, π-conjugated polymers are applied, and in particular, application to polymer organic solar cells is attracting attention. In particular, in an organic solar cell, it is desired to improve sunlight absorption efficiency, and it is important to develop a polymer that can absorb light having a long wavelength (600 nm or more).
Several examples have been reported in which a copolymer of a donor monomer and an acceptor monomer (hereinafter sometimes referred to as a copolymer) is used in a photoelectric conversion element for the purpose of increasing the absorption wavelength.

For example, Non-Patent Document 1 discloses that a copolymer having an imidothiophene skeleton and a benzodithiophene skeleton in the main chain absorbs light having a wavelength of about 700 nm, and the photoelectric conversion efficiency of a photoelectric conversion element using the copolymer is 6. It is described that it was about 8%.
Non-Patent Document 2 discloses that a copolymer having an imidothiophene skeleton and a dithienocyclopentadiene skeleton in the main chain absorbs light having a wavelength of about 700 nm, and the photoelectric conversion efficiency of a photoelectric conversion element using the copolymer is 3. It is described that it was about 1%.

Patent Document 1 describes that the photoelectric conversion efficiency of a photoelectric conversion element using a copolymer obtained by introducing a monomer such as a dithienosilol skeleton, a benzothiadiazole skeleton, or an imidobenzene skeleton into the main chain was about 0.7%. Yes.
Patent Document 2 discloses that a copolymer having a dithienosilole skeleton, a benzothiadiazole skeleton, etc. introduced into the main chain absorbs light having a wavelength of about 750 nm, and the photoelectric conversion efficiency of a photoelectric conversion element using the copolymer is about 3.5%. It is described that it was.

Patent Document 3 describes a photoelectric conversion element using a copolymer containing a biphenyl derivative skeleton and a thiophene skeleton having a substituent.
Non-Patent Document 3 uses a copolymer having an imidothiophene skeleton and a dithienocyclopentadiene skeleton introduced in the main chain, a copolymer containing an imidethiophene skeleton and a dithienosilole skeleton, and a copolymer having an imidethiophene skeleton and a dithienopyrrole skeleton introduced into the main chain. A photoelectric conversion element is described.

JP 2010-507233 A International Publication No. 2010/022058 JP 2006-63334 A

J. et al. Am. Chem. Soc. 2010, 132, 7595-7597 Xugang Guo, 5 others, Thieno [3,4-c] pyrrole-4,6-dione-Based Donor-Acceptor Conjugated Polymers for Solar Cells, [on line], Macromolecules, January 21, 2011 , Internet <URL: http: // pubs. acs. org / doi / pdfplus / 10.1021 / ma101878w> J. et al. Mater. Chem. 2011, 21, 3895-3902

  According to the study by the present inventors, none of the polymers described in the above-mentioned documents has sufficient coating film forming properties and conversion efficiency when used as a photoelectric conversion element, and further improvement has been demanded. .

As a result of intensive studies to solve the above problems, the inventors of the present invention contain a repeating unit composed of an imidothiophene skeleton and a dithienosilole skeleton, and a copolymer having a weight average molecular weight of 2 × 10 ⁴ or more and 1 × 10 ⁷ or less. The inventors have found that the material has both easy solubility practical for organic devices and a longer wavelength in the light absorption wavelength region, and has achieved the present invention. That is, this invention makes the following a summary.

[1] A copolymer having a repeating unit represented by the following general formula (1), having a polystyrene-equivalent weight average molecular weight of 2 × 10 ⁴ or more and 1 × 10 ⁷ or less.
(In the formula (1), R ¹ represents a substituent alkyl group which may have a which may have an optionally substituted alkenyl group or an optionally substituted aryl group, R ² to R ⁵ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, which may have an optionally substituted alkenyl group or an optionally substituted aryl group Represents.)
[2] An organic semiconductor material comprising the copolymer according to [1].
[3] An organic electronic device comprising the organic semiconductor material according to [2].
[4] A photoelectric conversion element in which an organic active layer is disposed between a pair of electrodes, wherein the organic active layer includes the organic semiconductor material according to [2].
[5] The organic semiconductor material is a fullerene compound, borane derivative, thiazole derivative, benzothiazole derivative, benzothiadiazole derivative, N-alkyl substituted naphthalene tetracarboxylic acid diimide, N-alkyl substituted perylene diimide derivative and n-type The photoelectric conversion device according to [4], comprising at least one n-type semiconductor compound selected from the group consisting of polymers.
[6] The photoelectric conversion device according to [4] or [5], further including a buffer layer containing a phosphine compound having a double bond with a Group 16 element.
[7] The photoelectric conversion element according to any one of [4] to [6], which is a solar cell.
[8] A solar cell module comprising the photoelectric conversion element according to [7].

  Since the copolymer of the present invention is easily soluble, it is a semiconductor material excellent in applicability to practical application processes. In addition, since the copolymer of the present invention has a longer light absorption wavelength region and high light absorption, an organic electronic device such as a solar cell using the copolymer has an advantage of high photoelectric conversion efficiency.

It is sectional drawing which shows typically the structure of the photoelectric conversion element as one Embodiment of this invention. It is sectional drawing which shows typically the structure of the solar cell as one Embodiment of this invention. It is sectional drawing which shows typically the structure of the solar cell module as one Embodiment of this invention. It is a figure which shows the absorption spectrum of the copolymer A1, the copolymer A2, the copolymer A3, and the copolymer B. It is a figure which shows the absorption spectrum of the copolymer A2 and the copolymer C. FIG. It is a figure which shows the X-ray-diffraction spectrum of copolymer A2.

Hereinafter, embodiments of the present invention will be described in detail.
The description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not specified in these contents unless it exceeds the gist.

The copolymer of the present invention has a repeating unit represented by the following formula (1), that is, a repeating unit composed of an imidothiophene skeleton and a dithienosilole skeleton. Moreover, the polystyrene equivalent weight average molecular weight is 2 × 10 ⁴ or more and 1 × 10 ⁷ or less. The copolymer of the present invention is preferable from the viewpoint that the light absorption wavelength region is longer and the light absorption is high.

In Formula (1), R ¹ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, R ² to R ⁵ each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group. To express.

Specific examples of groups and atoms in the definition of R ^{1 to} R ⁵ in formula (1) will be described below. R ¹ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent.

The number of carbon atoms of R ¹ is usually 1 or more, preferably 3 or more, more preferably 4 or more, and usually 20 or less, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.

  Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a cyclopropyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, a 3-methylbutyl group, and a cyclobutyl group. Group, pentyl group, cyclopentyl group, hexyl group, 2-ethylhexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, decyl group, cyclodecyl group, lauryl group or cyclolauryl Groups and the like. Among them, n-propyl group, iso-propyl group, cyclopropyl group, n-butyl group, iso-butyl group, tert-butyl group, 3-methylbutyl group, cyclobutyl group, pentyl group, cyclopentyl group, hexyl group, 2 -Ethylhexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, nonyl group, decyl group, lauryl group or cyclolauryl group are preferred, butyl group, pentyl group, hexyl group, 2-ethylhexyl group, cyclooctyl group, A nonyl group, a cyclononyl group, a decyl group, a cyclodecyl group, or the like is more preferable.

  The alkenyl group has usually 1 or more, preferably 3 or more, more preferably 4 or more, and usually 20 or less, preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less. Examples of such alkenyl groups include ethene, propene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, and the like. Group, hexadecene group, heptadecene group, octadecene group, nonadecene group, icocene group or geranyl group. Preferred are propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group or dodecene group, more preferably butene group, pentene group, hexene group, heptene group. An octene group, a nonene group or a decene group.

  The aryl group usually has 2 or more carbon atoms, on the other hand, usually 60 or less, preferably 20 or less, more preferably 14 or less. Examples of such an aryl group include an aromatic hydrocarbon group such as a phenyl group, a naphthalene group, an indane group, an indene group, a fluorene group, an anthracene group or an azulene group; a thienyl group, a furanyl group, a pyridyl group, a pyrimidyl group, And aromatic heterocyclic groups such as a thiazolyl group, an oxazolyl group, a triazolyl group, a benzothiophenyl group, a benzofuranyl group, a benzothienyl group, a benzothiazolyl group, a benzooxazolyl group, or a benzotriazolyl group. Of these, a phenyl group, a naphthalene group, a thienyl group, a pyridyl group, a pyrimidyl group, a thiazolyl group, or an oxazolyl group is preferable.

The substituent that the alkyl group, alkenyl group or aryl group may have is not particularly limited, but preferably a halogen atom, a hydroxyl group, a cyano group, an amino group, an ester group, an alkylcarbonyl group, an acetyl group, a sulfonyl group. Group, silyl group, boryl group, nitrile group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aromatic hydrocarbon group or aromatic heterocyclic group. These may be connected with adjacent substituents to form a ring. In particular, the substituent that the aryl group may have is a C _{1 to} C ₁₂ alkoxy group (“C _{1 to} C ₁₂ ” means that the organic group described together with this formula has 1 to 12 carbon atoms. indicates that. the same applies is less.) or _C 1 _{-C 12} alkyl group are preferable. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned. Among these, a fluorine atom is preferable.

As described above, in Formula (1), R ¹ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent. . By using R ¹ as these groups, it is preferable because the solubility of the copolymer in an organic solvent tends to be excellent, and it can be advantageous in a coating film forming process. More preferably, R ¹ is an alkyl group which may have a substituent or an aryl group which may have a substituent. The alkyl group is a linear, branched or cyclic alkyl group. Of these, a linear or branched alkyl group is preferable. Linear alkyl is preferable in that the crystallinity of the polymer can be improved, and thus mobility can be increased, and a branched alkyl group is preferable in that the solubility of the polymer can be improved. In addition, it is preferable that R ¹ is an aryl group which may have a substituent since the copolymer can absorb light having a longer wavelength. Furthermore, it is preferable that R ¹ is an aryl group which may have a substituent since the crystallinity of the polymer can be improved and the mobility can be increased.

R ^{2 to} R ⁵ may each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents an aryl group. As the alkyl group that may have a substituent, the alkenyl group that may have a substituent, and the aryl group that may have a substituent, the same groups as those described above for R ¹ may be used. Can be used. As the substituent that the alkyl group, alkenyl group, and aryl group may have, the same substituents as those described above for R ¹ can be used. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferable. R ^{2 to} R ⁵ may be bonded together to form a ring.

Of these, at least one of R ⁴ and R ⁵ is preferably an alkyl group or aryl group which may have a substituent, and both R ⁴ and R ⁵ may have a substituent. More preferably, it is an alkyl group or an aryl group. The reason why the alkyl group is preferable is that a linear alkyl group is preferable in that the mobility can be increased by improving the crystallinity of the polymer, and a branched alkyl group is preferable because the solubility of the polymer is improved. This is preferable in that film formation by a coating process is easy. It is preferable that at least one of R ⁴ and R ⁵ is an alkyl group from the viewpoint that the copolymer can absorb light having a longer wavelength. From these viewpoints, at least one of R ⁴ and R ⁵ is preferably a C _{1 to} C ₂₀ alkyl group, and particularly preferably a C _{6 to} C ₂₀ alkyl group. Further, being an aryl group is preferable in that the mobility between molecules tends to increase because the interaction between molecules is improved by the interaction between π electrons, and the stability of the dithienosilole skeleton tends to be improved. This is preferable.

From the viewpoint of improving the durability of the copolymer by increasing the steric hindrance around the silicon atom, R ⁴ and R ⁵ may have an alkyl group which may have a substituent or a substituent. It is preferably a good alkenyl group or an aryl group which may have a substituent.

From the viewpoint of improving the solubility of the copolymer, it is preferable that at least one of R ¹ and R ⁴ and R ⁵ is a linear or branched alkyl group, and R ¹ , R ⁴ , and R ⁵ are It is more preferable that it is a linear or branched alkyl group, and it is especially preferable that R ¹ , R ⁴ , and R ⁵ are branched alkyl groups. Here, the branched alkyl group is preferably a C _{3 to} C ₂₀ alkyl group, and more preferably a C _{6 to} C ₂₀ alkyl group.

From the viewpoint of strengthening the interaction between the copolymer molecules, it is preferable that at least one of R ¹ and R ⁴ and R ⁵ is a linear alkyl group or an aryl group, and R ¹ , R ⁴ , And R ⁵ is more preferably a linear alkyl group or an aryl group. It is particularly preferable in terms of mobility that R ¹ , R ⁴ , and R ⁵ are aryl groups, and that R ¹ , R ⁴ , and R ⁵ are linear alkyl groups indicates that the copolymer has a longer wavelength light. Is particularly preferred in that it can be absorbed. Here, it is more preferred straight-chain alkyl group is preferably a _C 1 _{-C 20} alkyl _group, a C 6 _{-C 20} alkyl group.

Moreover, it is preferable that at least one of R ² and R ³ is a halogen atom. This is preferable in that the heat resistance, weather resistance, chemical resistance, water / oil repellency and the like of the copolymer are improved.

  The copolymer of this invention may contain only 1 type of repeating units represented by Formula (1), and may contain 2 or more types. In that case, the type of repeating unit is not limited, but is usually 8 or less, preferably 5 or less. Moreover, you may contain another repeating unit in the range which does not impair the effect of this invention.

Although the preferable specific example of the copolymer of this invention is shown, it is not restricted to the following illustrations. C ₈ H ₁₇ and C ₄ H ₉ are linear alkyl groups having a predetermined number of carbon atoms. When the copolymer of the present invention includes a plurality of repeating units, the ratio between the plurality of repeating units included is arbitrary.

The copolymer of the present invention described above has an advantage of high photoelectric conversion characteristics because it has absorption in a long wavelength region (600 nm or more) and high open circuit voltage (Voc). In particular, it is a solar cell in combination with a fullerene compound. When applied to, it exhibits high solar cell characteristics. In addition, there is an advantage that the HOMO level is low and it is difficult to be oxidized.
Further, the copolymer of the present invention has an advantage of exhibiting high solubility. Since the solvent solubility at the time of coating film formation is high and the range of selection of the solvent itself is widened, it is easy to use a solvent that is optimal for the conditions, so that the film quality of the formed organic semiconductor layer can be improved. This is also considered to be a factor that the solar cell using this copolymer exhibits high solar cell characteristics.

The weight average molecular weight (Mw) in terms of polystyrene of the copolymer of the present invention is 2 × 10 ⁴ or more, preferably 2.5 × 10 ⁴ or more, more preferably 3.0 × 10 ⁴ or more, and further preferably 3.5 ×. 10 ⁴ or more, still more preferably 4.0 × 10 ⁴ or more, and particularly preferably 5.0 × 10 ⁴ or more. On the other hand, preferably 1 × 10 ⁷ or less, more preferably 1 × 10 ⁶ or less, even more preferably 9 × 10 ⁵ or less, even more preferably 5 × 10 ⁵ or less, even more preferably 1 × 10 ⁵ or less, and even more preferably Preferably it is 8 × 10 ⁴ or less, particularly preferably 6 × 10 ⁴ or less. This range is preferable in terms of increasing the light absorption wavelength and increasing the absorbance.

  The weight average molecular weight in terms of polystyrene of the copolymer of the present invention can be determined by gel permeation chromatography (GPC). Specifically, Shim-pack GPC-803 and GPC-804 (manufactured by Shimadzu Corporation, inner diameter 8.0 mm, length 30 cm) are connected in series as columns, and LC-10AT is used as a pump. It can be measured by using a CTO-10A as an oven, a differential refractive index detector (manufactured by Shimadzu Corporation: RID-10A), and a UV-vis detector (manufactured by Shimadzu Corporation: SPD-10A) as a detector. The copolymer to be measured is dissolved in tetrahydrofuran (THF), and 5 μL of the resulting solution is injected into the column. Measurement is performed at a flow rate of 1.0 mL / min using THF as the mobile phase. LC-Solution (Shimadzu Corporation) is used for the analysis.

The number average molecular weight of the copolymer of the present invention (Mn) of usually 1.0 × 10 ³ or more, preferably 3.0 on × 10 ^3, more preferably 5.0 × 10 ³ or more, more preferably 1.0 × It is 10 ⁴ or more, more preferably 1.5 × 10 ⁴ or more, particularly preferably 2.0 × 10 ⁴ or more, and particularly preferably 2.5 × 10 ⁴ or more. On the other hand, it is preferably 1 × 10 ⁸ or less, more preferably 1 × 10 ⁷ or less, and further preferably 9 × 10 ⁶ or less. The number average molecular weight is preferably in this range from the viewpoint of increasing the light absorption wavelength and achieving high absorbance. The number average molecular weight of the copolymer of the present invention can be measured by the same method as the above weight average molecular weight.

  The molecular weight distribution (PDI, (weight average molecular weight / number average molecular weight (Mw / Mn))) of the copolymer of the present invention is usually 1.0 or more, preferably 1.1 or more, more preferably 1.2 or more, even more preferably. Is 1.3 or more. On the other hand, it is preferably 20.0 or less, more preferably 15.0 or less, and still more preferably 10.0 or less. The molecular weight distribution is preferably in this range in that the solubility of the copolymer can be in a range suitable for coating. The molecular weight distribution of the copolymer of the present invention can be measured by the same method as the above weight average molecular weight.

The copolymer of the present invention preferably has a light absorption maximum wavelength (λ _max ) of usually 470 nm or more, preferably 480 nm or more, and is usually 1200 nm or less, preferably 1000 nm or less, more preferably 900 nm or less. Moreover, a half value width is 10 nm or more normally, Preferably it is 20 nm or more, on the other hand, it is 300 nm or less normally.
Moreover, when using the copolymer of this invention for a solar cell use, it is so desirable that the absorption wavelength range of a copolymer is near the absorption wavelength range of sunlight.

The solubility of the copolymer of the present invention is not particularly limited, but preferably the solubility in chlorobenzene at 25 ° C. is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, On the other hand, it is usually 30% by weight or less, preferably 20% by weight. Increased solubility is preferable because a film can be formed with a sufficient thickness.
Here, the solvent that can be used in the film formation described later is not particularly limited as long as it can uniformly dissolve or disperse the copolymer. For example, aliphatic carbonization such as hexane, heptane, octane, isooctane, nonane or decane. Hydrogens; aromatic hydrocarbons such as toluene, xylene, chlorobenzene or orthodichlorobenzene; lower alcohols such as methanol, ethanol or propanol; ketones such as acetone, methyl ethyl ketone, cyclopentanone or cyclohexanone; ethyl acetate, butyl acetate Or esters such as methyl lactate; halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane or trichloroethylene; ethers such as ethyl ether, tetrahydrofuran or dioxane Amides such as dimethylformamide or dimethylacetamide, and the like. Among these, aromatic hydrocarbons such as toluene, xylene, chlorobenzene or orthodichlorobenzene, and halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane or trichloroethylene are preferable.

  The copolymer of the present invention preferably interacts between molecules. In the present specification, the interaction between molecules means that the distance between polymer chains is shortened due to the interaction of π-π stacking between molecules. The stronger the interaction, the higher the mobility and / or crystallinity. That is, in a copolymer that interacts between molecules, electron transfer between molecules is likely to occur. Therefore, when this copolymer is used in the active layer 103 in a photoelectric conversion element described later, the p-type semiconductor compound in the active layer 103 is used. It is considered that holes generated at the interface of the mixture layer of the n-type semiconductor compound and the n-type semiconductor compound can be efficiently transported to the electrode (anode) 101.

  An example of a crystallinity measuring method is an X-ray diffraction method (XRD). In this specification, having crystallinity means that the diffraction peak of the copolymer is shown in the X-ray diffraction spectrum, and it is particularly preferable that the diffraction peak is shown in the vicinity of 2θ = 4.8 °. Having crystallinity is considered to mean that it has a laminated structure in which molecules are arranged, and is preferable in that the active layer described later tends to be thickened. The X-ray diffraction method (XRD) can be performed based on a method described in a publicly known document (X-ray crystal analysis guide (applied physics selection book 4)).

The hole mobility of the copolymer of the present invention is usually 1.0 × 10 ⁽⁻⁷⁾ cm ² / (Vs) or more, preferably 1.0 × 10 ⁽⁻⁶⁾ cm ² / (Vs) or more, more preferably Is 1.0 × 10 ⁽⁻⁵⁾ cm ² / (Vs) or more, particularly preferably 1.0 × 10 ⁽⁻⁴⁾ cm ² / (Vs) or more. On the other hand, the hole mobility of the copolymer of the present invention is usually 1.0 × 10 ⁽³⁾ cm ² / (Vs) or less, preferably 1.0 × 10 ⁽²⁾ cm ² / (Vs) or less. More preferably, it is 1.0 × 10 ⁽¹⁾ cm ² / (Vs) or less. In order to obtain high conversion efficiency, it is important to balance the mobility of the n-type semiconductor and the mobility of the copolymer. The hole mobility of the copolymer of the present invention is preferably in this range from the viewpoint of bringing the mobility of the copolymer of the present invention used as a p-type semiconductor close to the mobility of the n-type semiconductor. As a method for measuring the hole mobility, there is an FET method. The FET method can be performed by a method described in a known document (Japanese Patent Application Laid-Open No. 2010-045186).

  The impurities in the copolymer of the present invention are preferably as few as possible. In particular, if a transition metal catalyst such as palladium or copper remains, an exciton trap due to the heavy atom effect of the transition metal is generated, so that charge transfer is hindered. As a result, the photoelectric conversion efficiency when used in a photoelectric conversion element is reduced. May decrease. The concentration of the transition metal catalyst is usually 1000 ppm or less, preferably 500 pm or less, more preferably 100 ppm or less, per 1 g of copolymer. On the other hand, it is usually greater than 0 ppm, preferably 1 ppm or more, more preferably 3 ppm or more.

  The residual amount of the terminal residue of the copolymer (X and Y in formula (2) and formula (3) described later) is not particularly limited, but is usually 6000 ppm or less, preferably 4000 ppm or less, more preferably 4,000 ppm or less per gram of copolymer. Is at most 3000 ppm, more preferably at most 2000 ppm, even more preferably at most 1000 ppm, particularly preferably at most 500 ppm, most preferably at most 200 ppm. On the other hand, it is usually greater than 0 ppm, preferably 1 ppm or more, more preferably 3 ppm or more.

  In particular, the residual amount of Sn element in the copolymer is usually 5000 ppm or less, preferably 4000 ppm or less, more preferably 2500 ppm or less, more preferably 1000 ppm or less, even more preferably 750 ppm or less, particularly preferably 500 ppm or less per 1 g of the copolymer. Most preferably, it is 100 ppm or less. On the other hand, it is usually greater than 0 ppm, preferably 1 ppm or more, more preferably 3 ppm or more. It is preferable to set the remaining amount of Sn atoms to 5000 ppm or less because the remaining amount of Sn element in the alkylstannyl group which is easily thermally decomposed is reduced, and high performance can be obtained from the viewpoint of stability.

  Further, the residual amount of halogen element is usually 5000 ppm or less, preferably 4000 ppm or less, more preferably 2500 ppm or less, further preferably 1000 ppm or less, even more preferably 750 ppm or less, particularly preferably 500 ppm or less, most preferably per 1 g of copolymer. 100 ppm or less. On the other hand, it is usually greater than 0 ppm, preferably 1 ppm or more, more preferably 3 ppm or more. It is preferable that the residual amount of the halogen element is 5000 ppm or less because the performance of the copolymer such as photoelectric conversion characteristics and durability tends to be improved.

The residual amount of the terminal residues (X and Y described later) of the copolymer can be identified by elements other than carbon, hydrogen and nitrogen. As a measurement method, elemental analysis of the obtained high molecular weight body can be carried out for bromine ions (Br ⁻ ) and iodine ions (I ⁻ ) by ion chromatography or ICP mass spectrometry, and for Pd and Sn Can be performed by ICP mass spectrometry.

  The ion chromatography method can be carried out by a method described in a known document (“ion chromatography”: Kyoritsu Shuppan Co., Ltd.). For example, it can be carried out by an ion chromatograph analyzer (Dionex Corporation ion chromatograph analyzer DX120 type or DX500 type).

ICP mass spectrometry can be carried out by a method described in a known document (“Plasma ion source mass spectrometry” (Academic Publishing Center)). Specifically, with respect to Pd and Sn, after wet decomposition of the sample, Pd and Sn in the decomposition solution are quantified by a calibration curve method using an ICP mass spectrometer (ICP mass spectrometer 7500ce type manufactured by Agilent Technologies). Can do. For Br ⁻ and I ⁻ , the sample is combusted with a sample combustion device (sample combustion device QF-02 type manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the combustion gas is absorbed in an alkaline absorbing liquid containing a reducing agent. Br ⁻ and I ⁻ in the medium can be quantified by a calibration curve method using an ICP mass spectrometer (ICP mass spectrometer 7500ce type manufactured by Agilent Technologies).

(Method for producing the copolymer of the present invention)
The method for producing the copolymer of the present invention is not particularly limited. For example, the copolymer can be produced by a known method using an imidothiophene derivative and a dithienosilole derivative. As a preferred method, an imidothiophene derivative compound represented by the following general formula (2) and a dithienosilole derivative compound represented by the following general formula (3) are polymerized in the presence of an appropriate catalyst if necessary. The method of doing is mentioned.

In formula (2), R ¹ has the same meaning as described above. In formula (3), R ^{2 to} R ⁵ are as defined above.
X and Y are each independently a halogen atom, alkylstannyl group, alkylsulfo group, arylsulfo group, arylalkylsulfo group, boric acid ester residue, sulfoniummethyl group, phosphoniummethyl group, phosphonatemethyl group, monohalogen Represents a methyl group, a boric acid residue (—B (OH) ₂ ), a formyl group, an alkenyl group or an alkynyl group. From the viewpoint of synthesis of the compound represented by the formula (2) or (3) and the viewpoint of easy reaction, X and Y are each independently a halogen atom, an alkylstannyl group, a borate ester residue. Or a boric acid residue (—B (OH) ₂ ). In X and Y, the halogen atom is preferably a bromine atom or an iodine atom.

  Examples of the boric acid ester residue include a group represented by the following formula.

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)
Examples of the alkylstannyl group include groups represented by the following formulas.

As an alkenyl group, a C2-C12 alkenyl group is mentioned, for example.
The reaction method used for the polymerization of the copolymer of the present invention includes Suzuki-Miyaura cross-coupling reaction method, Stille coupling reaction method, Yamamoto coupling reaction method, Grignard reaction method, Heck reaction method, Sonogashira reaction method, FeCl _{3 and the} like. A reaction method using an oxidizing agent, a method using an electrochemical oxidation reaction, a reaction method by decomposition of an intermediate compound having an appropriate leaving group, and the like. Among these, the Suzuki-Miyaura coupling reaction method, the Stille coupling reaction method, the Yamamoto coupling reaction method, and the Grignard reaction method are preferable in terms of easy structure control. In particular, the Suzuki-Miyaura cross-coupling reaction method, the Stille coupling reaction method, and the Grignard reaction method are preferable from the viewpoint of easy availability of materials and easy reaction operation. These reactions are described in "Cross Coupling-Fundamentals and Industrial Applications (CMC Publishing)", "Transition Metal Catalyzed Reactions for Organic Synthesis (edited by Jiro Jiro: edited by Organic Synthetic Chemistry Association)", "For Organic Synthesis" The reaction can be carried out according to a method described in known literature such as “catalytic reaction 103 (Teijiro Hatakeyama: Tokyo Kagaku Dojin)”. The following describes the Stille coupling reaction method.

  When the Stille coupling reaction method is used, in the general formulas (2) and (3), for example, X is a halogen atom and Y is an alkylstannyl group, X is an alkylstannyl group, and Y is It is preferably a halogen atom.

  The amount ratio of the dithienosilole derivative represented by the formula (3) to the imidothiophene derivative represented by the formula (2) is usually 0.90 or more, preferably 0.95 or more in terms of molar ratio, Usually, it is 1.3 or less, preferably 1.2 or less. By being in the said range, it is preferable at the point which acquires a high molecular weight body with a higher yield.

  When the copolymer of the present invention is used as a material for an organic photoelectric conversion device, since the device characteristics are good when the purity is high, the monomer before polymerization (imidothiophene derivative compound represented by the general formula (2), and general The dithienosilole derivative compound represented by the formula (3) is preferably subjected to a coupling reaction after purification by a method such as distillation, sublimation purification, column chromatography, or recrystallization.

  When the copolymer of the present invention is used as a material for an organic photoelectric conversion element, the purity of the monomer is usually 90% or more, preferably 95% or more. A high purity of the monomer is preferable because the device characteristics of the photoelectric conversion device having the copolymer of the present invention are improved.

In the polymerization, an alkali, a catalyst, a cocatalyst, an organic ligand, a phase transfer catalyst, or the like can be appropriately added to promote the polymerization. These alkalis and catalysts may be selected according to the type of polymerization, but those that are sufficiently soluble in the solvent used for the polymerization reaction are preferred. Examples of the alkali include inorganic bases such as potassium carbonate, sodium carbonate and cesium carbonate; organic bases such as triethylamine. Examples of the catalyst include a palladium complex containing a phosphine compound such as tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ) as a ligand or a palladium (Pd) catalyst such as palladium acetate; Ni (dppp) Cl ₂ or Ni (dppe) nickel catalyst such as Cl _2; iron catalyst such as iron chloride; copper catalyst such as copper iodide and the like.

As a palladium complex containing a phosphine compound as a ligand, specifically, Pd (PPh ₃ ) ₄ , Pd (P (o-tolyl) ₃ ) ₄ , Pd (PCy ₃ ) ₂ , Pd ₂ (dba) _{3 ,} PdCl ₂ (PPh ₃ )) _{2 and the} like (wherein Ph represents a phenyl group, Cy represents a cyclohexyl group, o-toyl represents a 2-tolyl group, and dba represents dibenzylideneacetone). . When a divalent Pd complex such as Pd ₂ (dba) _{3 or} PdCl ₂ (PPh ₃ )) ₂ is used, it may be used in combination with an organic ligand such as PPh ₃ or P (o-tolyl) _3. desirable.

The amount of the catalyst used is usually 1 × 10 ⁻⁴ mol% or more, preferably the amount of the palladium complex based on the total of the imidothiophene derivative represented by the formula (2) and the dithienosilole derivative represented by the formula (3). Is 1 × 10 ⁻³ mol% or more, more preferably 1 × 10 ⁻² mol% or more, and usually 1 × 10 ² mol% or less, more preferably 5 mol% or less. It is preferable that the amount of the catalyst used be in this range because a higher molecular weight copolymer tends to be obtained at a lower cost and a higher yield.

Examples of the cocatalyst include inorganic salts such as cesium fluoride, copper oxide, and copper halide. The amount of the co-catalyst used is usually 1 × 10 ⁻⁴ mol% or more, preferably 1 × 10 ⁻³ mol% or more, more preferably 1 × 10 ^{− − based on the} imidothiophene derivative represented by the formula (2). ² is a mol% or more, whereas, usually 1 × ¹⁰ 4 mol% or less, preferably 1 × ¹⁰ 3 mol% or less, more preferably 1.5 × ¹⁰ 2 mol% or less. It is preferable that the amount of the cocatalyst used be in this range because the copolymer tends to be obtained at a lower cost and with a higher yield.

Examples of the phase transfer catalyst include tetraethylammonium hydroxide and Aliquat 336 (manufactured by Aldrich). The amount of the phase transfer catalyst used is usually 1 × 10 ⁻⁴ mol% or more, preferably 1 × 10 ⁻³ mol% or more, more preferably 1 × 10 ^{4 with} respect to the imidothiophene derivative represented by the formula (2). ^-2 mol% or more, and usually 5 mol% or less, more preferably 3 mol% or less. It is preferable that the amount of the phase transfer catalyst used is in this range because the copolymer tends to be obtained at a lower cost and in a higher yield.

  Examples of the solvent used in the polymerization reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; chlorobenzene, dichlorobenzene, and trichlorobenzene. Halogenated aromatic hydrocarbons; alcohols such as methanol, ethanol, propanol, isopropanol, butanol or t-butyl alcohol; water; ethers such as dimethyl ether, diethyl ether, methyl t-butyl ether, tetrahydrofuran, tetrahydropyran or dioxane; Examples include aprotic organic solvents such as DMF. These solvents may be used alone or in combination of two or more.

The amount of the solvent used is usually 1 × 10 ⁻² mL or more, preferably 1 × with respect to 1 g in total of the imidothiophene derivative represented by formula (2) and the dithienosilole derivative represented by formula (3). It is 10 ⁻¹ mL or more, more preferably ¹ mL or more, while it is usually 1 × 10 ⁵ mL or less, preferably 1 × 10 ³ mL or less, more preferably 2 × 10 ² mL or less. The reaction temperature of the Stille coupling reaction is usually 0 ° C. or higher, preferably 20 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 60 ° C. or higher. On the other hand, it is usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, and particularly preferably 160 ° C. or lower. The heating method is not particularly limited, and examples thereof include oil bath heating, thermocouple heating, infrared heating, microwave heating, heating by contact using an IH heater, and the like. The reaction time is usually 1 minute or longer, preferably 10 minutes or longer, and is usually 160 hours or shorter, preferably 120 hours or shorter, more preferably 100 hours or shorter. By carrying out the reaction under these reaction conditions, the copolymer can be obtained in a shorter time and with a higher yield.

  After the polymerization reaction, for example, a crude polymer can be obtained by ordinary post-treatment such as extraction with an organic solvent after quenching with water and evaporation of the organic solvent. After the synthesis of the polymer, purification treatment such as reprecipitation purification, Soxhlet, gel permeation chromatography or metal removal by scavenger is preferred.

The Stille coupling reaction is preferably performed in a nitrogen (N ₂ ) or argon (Ar) atmosphere.

  For the copolymer after the polymerization reaction, it is preferable to perform terminal treatment of the copolymer. By carrying out terminal treatment of the copolymer, it is possible to reduce the residual amount of halogen residues such as bromine (Br) and iodine (I) and terminal residues (the above X and Y) such as alkylstannyl groups of the copolymer. is there. This end treatment is preferable because a polymer having better performance in terms of efficiency and durability can be obtained.

  The method for terminal treatment of the copolymer is not particularly limited, but the following methods can be mentioned. When the copolymer is polymerized by a Stille coupling reaction, a terminal treatment can be performed on halogen elements such as bromine (Br) and iodine (I) and alkylstannyl groups present at the terminal of the copolymer.

The terminal treatment method of the halogen element can be performed by adding aryltrialkyltin as a terminal treatment agent to the reaction system and then stirring with heating. Examples of the aryl trialkyl tin include phenyl trimethyl tin and thienyl trimethyl tin. The addition amount of the end treatment agent is not particularly limited, but is usually 1.0 × 10 ⁻² equivalent or more, preferably 0.1 equivalent or more, more preferably 1 equivalent or more with respect to the halogen-terminated terminal addition monomer. On the other hand, it is usually 50 equivalents or less, preferably 20 equivalents or less, more preferably 10 equivalents or more. The heating time is not particularly limited, but is usually 30 minutes or longer, preferably 1 hour or longer, and is usually 50 hours or shorter, preferably 20 hours or shorter. By performing the reaction under these reaction conditions, the terminal treatment can be performed in a shorter time and with a higher conversion rate.

  It is preferable that the terminal treatment of the halogen element is performed and the terminal is substituted with an aryl group, so that the copolymer becomes more stable due to the conjugate stability effect.

As a terminal treatment method for the alkylstannyl group, an aryl halide can be added as a terminal treatment agent to the reaction system, and then heated and stirred. Examples of the aryl halide include iodothiophene, iodobenzene, bromothiophene, and bromobenzene. The addition amount of the end treatment agent is not particularly limited, but is usually 1.0 × 10 ⁻² equivalent or more, preferably 0.1 equivalent or more, more preferably 1 with respect to the alkylstannyl group terminal addition monomer. On the other hand, it is usually 50 equivalents or less, preferably 20 equivalents or less, more preferably 10 equivalents or more. The heating time is not particularly limited, but is usually 30 minutes or longer, preferably 1 hour or longer, and is usually 50 hours or shorter, preferably 10 hours or shorter. By performing the reaction under these reaction conditions, the terminal treatment can be performed in a shorter time and with a higher conversion rate.

  When the terminal of the alkylstannyl group is treated and the terminal is substituted with an aryl group, the Sn element in the alkylstannyl group, which is prone to thermal decomposition, does not exist in the polymer, so the deterioration of the copolymer over time is suppressed. Expected to be. Moreover, it is preferable that the terminal is substituted with an aryl group in that the copolymer can be more stable due to the conjugate stability effect.

Although there is no special restriction | limiting about operation of said terminal treatment, It is preferable to carry out each independently. In addition, there is no special restriction | limiting in the operation order of each terminal process, It can select suitably.
The terminal treatment may be performed before the copolymer is purified or after the copolymer is purified.

  When the end treatment is performed after copolymer purification, the copolymer and one end treatment agent (aryl halide or aryltrimethyltin) are dissolved in an organic solvent, a transition metal catalyst such as a palladium catalyst is added, and the mixture is heated and stirred under nitrogen. The other end treatment agent (aryltrimethyltin or aryl halide) is added and the mixture is heated and stirred. By performing the above treatment, the terminal residue can be efficiently removed in a short time, which is preferable.

The addition amount of the transition metal catalyst such as a palladium catalyst is not particularly limited, but is usually 5.0 × 10 ⁻³ equivalent or more, preferably 1.0 × 10 ⁻² equivalent or more, relative to the copolymer, On the other hand, it is usually 1.0 × 10 ⁻¹ equivalent or less, preferably 5.0 × 10 ⁻² equivalent or less. When the addition amount of the catalyst is within this range, the end treatment can be performed at a lower cost and at a higher conversion rate.
The addition amount of the alkylstannyl group terminal treating agent is not particularly limited, but is usually 1.0 × 10 ⁻² equivalent or more, preferably 1.0 × 10 6 with respect to the alkylstannyl group terminal addition monomer. ^-1 equivalent or more, more preferably 1 equivalent or more, and usually 50 equivalents or less, preferably 20 equivalents or less, more preferably 10 equivalents or more. When the added amount of the end treatment agent is within this range, the end treatment can be performed at a lower cost and at a higher conversion rate.

The addition amount of the halogen group terminal treating agent is not particularly limited, but is usually 1.0 × 10 ⁻² equivalent or more, preferably 1.0 × 10 ⁻¹ equivalent, based on the halogen group terminal addition monomer. As mentioned above, More preferably, it is 1 equivalent or more, On the other hand, Usually, it is 50 equivalent or less, Preferably it is 20 equivalent or less, More preferably, it is 10 equivalent or more. When the added amount of the end treatment agent is within this range, the end treatment can be performed at a lower cost and at a higher conversion rate.
The heating time is not particularly limited, but is usually 30 minutes or longer, preferably 1 hour or longer, and is usually 25 hours or shorter, preferably 10 hours or shorter.

  In addition, when a copolymer is polymerized by the Suzuki-Miyaura cross-coupling reaction method, a method of heating and stirring after adding arylboronic acid can be mentioned as a terminal treatment method.

  As described above, the purification can be performed by a method such as soxhlet, gel permeation chromatography, or metal removal by a scavenger.

  In addition, the imide thiophene derivative (imide thiophene monomer) of the formula (2) used as a raw material for the polymerization reaction is described in J. Am. Am. Chem. Soc. 2010, 132 (22), 7595-7597. Further, dithienosilole derivatives of formula (3) (dithienosilole monomers) are described in J. Org. Mater. Chem. , 2011, 21, 3895, and J.A. Am. Chem. Soc. 2008, 130, 16144-16145.

(Organic semiconductor materials)
The copolymer of the present invention is suitable as an organic semiconductor material because it has high solvent solubility and high light absorption in a long wavelength region.

  The organic semiconductor material of the present invention is characterized by containing at least the copolymer. One type of the copolymer of the present invention may be contained alone, or two or more types may be contained in any combination. Moreover, although it may consist only of the copolymer of this invention, the other component (For example, another polymer, a monomer, various additives, etc.) may be contained.

  The organic semiconductor material of the present invention is suitable for an organic semiconductor layer (organic active layer) of an organic electronic device described later. In that case, the organic semiconductor material is preferably used after being formed into a film, and physical properties such as the above-described solubility in an organic solvent and excellent workability appear as preferable points. Details of use as an organic semiconductor layer of an organic electronic device will be described later.

The organic semiconductor material of the present invention functions sufficiently as a material for an organic semiconductor layer of an organic electronic device alone, but can also be used by mixing and / or laminating with other organic semiconductor materials. Other organic semiconductor materials that can be used in combination with the organic semiconductor material of the present invention include Poly (3-hexylthiophene) (P3HT), Poly [2,6- (4,4-bis- [2-ethylhexyl] -4H-cyclenta). [2,1-b: 3,4-b ′] dithiophene) -alt-4,7- (2,1,3-benzothiazole)] (PCPDTBT), benzoporphyrin (BP), pentacene, and n-type semiconductor compounds as known perylene - _{bisimide, [6,6] -Phenyl-C 61} -butyric acid methyl ester ([60] PCBM) or PCBM with a larger fullerene such as _{C 70,} [6,6] -Phenyl- C ₆₁ -butyric acid -Butyl ester ([60] PCBNB) or PCBNB having a larger fullerene such as _{C 70,} although the known organic semiconductor materials such as fullerene derivatives and the like, are not particularly limited thereto.

The organic semiconductor material of the present invention exhibits semiconductor characteristics. For example, in field effect mobility measurement, the hole mobility is usually 1.0 × 10 ⁻⁵ cm ² / Vs or more, preferably 1.0 × 10 ⁻⁴ cm. ² / Vs or more, while the hole mobility is usually 1.0 × 10 ⁴ cm ² / Vs or less, preferably 1.0 × 10 ³ cm ² / Vs or less, more preferably 1.0 × 10 ^2. cm ² / Vs or less. As a method for measuring the hole mobility, there is an FET method. The FET method can be performed by a method described in publicly known literature (Japanese Patent Application Laid-Open No. 2010-045186).

(Organic electronic devices)
Next, the organic electronic device of the present invention will be described.
The organic electronic device of the present invention is characterized by being formed using the organic semiconductor material of the present invention described above. If the organic semiconductor material of this invention is applicable, there will be no restriction | limiting in particular in the kind of organic electronic device. Examples include a light emitting element, a switching element, a photoelectric conversion element, an optical sensor using photoelectric conductivity, and the like.

Examples of the light emitting element include various light emitting elements used for display devices. Specific examples include a liquid crystal display element, a polymer dispersion type liquid crystal display element, an electrophoretic display element, an electroluminescent element, an electrochromic element, and the like.
Specific examples of the switching element include a diode (pn junction diode, Schottky diode, MOS diode, etc.), a transistor (bipolar transistor, field effect transistor (FET), etc.), a thyristor, and a composite element thereof (for example, TTL). Etc.).

Specific examples of the photoelectric conversion element include a thin film solar cell, a charge coupled device (CCD), a photomultiplier tube, and a photocoupler. Moreover, what utilized these photoelectric conversion elements is mentioned as an optical sensor using photoelectric conductivity.
Which part of the organic electronic device the organic semiconductor material of the present invention is used is not particularly limited, and can be used in any part. Particularly in the case of a photoelectric conversion element, the organic semiconductor layer containing the organic semiconductor material of the present invention is usually used as an organic active layer of an organic electronic device.

<Photoelectric conversion element>
The photoelectric conversion element according to the present invention has at least an organic active layer and a pair of electrodes, and the organic active layer contains the organic semiconductor material of the present invention. The organic active layer and the buffer layer are disposed between the electrodes. Although FIG. 1 shows the photoelectric conversion element used for a general organic thin film solar cell, it is not necessarily restricted to this.
The photoelectric conversion element 107 as one embodiment of the present invention includes a substrate 106, an anode 101, a hole extraction layer 102, an organic active layer 103 (a mixed layer of p-type semiconductor compound and n-type semiconductor compound), an electron extraction layer 104, a cathode. 105 has a sequentially formed layer structure. Other layers may be inserted between the respective layers to the extent that the functions of the layers described later are not affected.

<Active layer 103>
In the photoelectric conversion element according to the present invention, the active layer 103 refers to a layer in which photoelectric conversion is performed, and includes a p-type semiconductor compound and an n-type semiconductor compound. When the photoelectric conversion element 107 receives light, the light is absorbed by the active layer 103, electricity is generated at the interface between the p-type semiconductor compound and the n-type semiconductor compound, and the generated electricity is extracted from the electrodes 101 and 105.

  The active layer 103 may use either an inorganic compound or an organic compound, but is preferably a layer that can be formed by a simple coating process. More preferably, the active layer 103 is an organic active layer made of an organic compound. In the following description, it is assumed that the active layer 103 is an organic active layer.

  The layer structure of the organic active layer is a thin film laminated type in which a p-type semiconductor compound and an n-type semiconductor compound are laminated, a bulk heterojunction type in which a p-type semiconductor compound and an n-type semiconductor compound are mixed, and a p-type in an intermediate layer of a thin film laminated type. Examples include a structure having a layer (i layer) in which a semiconductor compound and an n-type semiconductor compound are mixed. Among these, a bulk heterojunction type in which a p-type semiconductor compound and an n-type semiconductor compound are mixed is preferable.

The thickness of the organic active layer 103 is not particularly limited, but is usually 10 nm or more, preferably 50 nm or more, while usually 1.0 × 10 ³ nm or less, preferably 5.0 × 10 ² nm or less, more preferably 2 0.0 × 10 ² nm or less. It is preferable that the thickness of the organic active layer is 10 nm or more because uniformity is maintained and short-circuiting is less likely to occur. Further, it is preferable that the thickness of the organic active layer is 1.0 × 10 ³ nm or less because the internal resistance is reduced and the distance between the electrodes is not increased, and the charge diffusion is improved.

  A method for forming the organic active layer 103 is not particularly limited, but a coating method is preferable. The coating method can be performed by any of the following methods. Examples include reverse roll coating, gravure coating, kiss coating, roll brushing, spray coating, air knife coating, wire barber coating, pipe doctor method, impregnation / coating method, curtain coating method and the like.

[P-type semiconductor compound]
The p-type semiconductor compound according to the present invention contains at least the copolymer of the present invention, but may be mixed and / or laminated with other organic semiconductor materials. Hereinafter, organic semiconductor materials that can be used in combination, for example, high-molecular organic semiconductor materials and low-molecular organic semiconductor materials will be described.

<High molecular organic semiconductor compound>
The polymer organic semiconductor compound that can be used in the present invention is not particularly limited, and is a conjugated copolymer semiconductor such as polythiophene, polyfluorene, polyphenylene vinylene, polythienylene vinylene, polyacetylene, or polyaniline; an alkyl group or other substituent is substituted. Also included are copolymer semiconductors such as oligothiophene. Moreover, the semiconductor copolymer which copolymerized 2 or more types of monomer units is also mentioned. Conjugated copolymers are described in, for example, Handbook of Conducting Polymers, 3 ^rd Ed. (2 volumes), 2007, Materials Science and Engineering, 2001, 32, 1-40, Pure Appl. Chem. Use a copolymer described in publicly known literature such as 2002, 74, 2031-3044, Handbook of THIOPHENE-BASED MATERIALS (2 volumes), 2009, or a derivative thereof, and a copolymer that can be synthesized by a combination of the described monomers. Can do.

  One kind of compound or a mixture of plural kinds of compounds may be used. Specific examples of the polymer organic semiconductor compound that can be used in combination include the following, but are not limited thereto.

<Low molecular organic semiconductor compounds>
The low-molecular organic semiconductor compound that can be used in the present invention is not particularly limited, but specifically, condensed aromatic hydrocarbons such as naphthacene, pentacene or pyrene; four thiophene rings such as α-sexithiophene Oligothiophenes containing above: those containing at least one of thiophene ring, benzene ring, fluorene ring, naphthalene ring, anthracene ring, thiazole ring, thiadiazole ring and benzothiazole ring, and a total of four or more linked; phthalocyanine compound And a metal complex thereof, or a porphyrin compound such as tetrabenzoporphyrin and a macrocycle compound thereof such as a metal complex thereof. Preferably, they are a phthalocyanine compound and its metal complex, or a porphyrin compound and its metal complex.

  Examples of the porphyrin compound and its metal complex (Q in the figure are CH), the phthalocyanine compound and its metal complex (Q in the figure are N) include compounds having the following structures.

Here, M represents a metal or two hydrogen atoms. As the metal, in addition to a divalent metal such as Cu, Zn, Pb, Mg, Co or Ni, a trivalent or higher metal having an axial ligand. Examples thereof include TiO, VO, SnCl ₂ , AlCl, InCl, and Si.
Y ^{1 to} Y ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. The alkyl group having 1 to 24 carbon atoms is a saturated or unsaturated chain hydrocarbon group having 1 to 24 carbon atoms or a saturated or unsaturated cyclic hydrocarbon group having 3 to 24 carbon atoms. Among these, a saturated or unsaturated chain hydrocarbon group having 1 to 12 carbon atoms or a saturated or unsaturated cyclic hydrocarbon group having 3 to 12 carbon atoms is preferable.

  Among phthalocyanine compounds and metal complexes thereof, preferably 29H, 31H-phthalocyanine, copper phthalocyanine complex, zinc phthalocyanine complex, magnesium phthalocyanine complex, lead phthalocyanine complex, titanium phthalocyanine oxide complex, vanadium phthalocyanine oxide complex, indium phthalocyanine halogen complex, gallium Phthalocyanine halogen complex, aluminum phthalocyanine halogen complex, tin phthalocyanine halogen complex, silicon phthalocyanine halogen complex, or copper 4,4 ′, 4 ″, 4 ′ ″-tetraaza-29H, 31H-phthalocyanine complex, more preferably Titanium phthalocyanine oxide complex, vanadium phthalocyanine oxide complex, indium phthalocyanine chloro complex, aluminum fluoride Russia is a Nin chloro complexes. In addition, the above kind of compound or a mixture of plural kinds of compounds may be used.

  Among the porphyrin compounds and metal complexes thereof, 5,10,15,20-tetraphenyl-21H, 23H-porphine, 5,10,15,20-tetraphenyl-21H, 23H-porphine cobalt (II), 5,10,15,20-tetraphenyl-21H, 23H-porphine copper (II), 5,10,15,20-tetraphenyl-21H, 23H-porphine zinc (II), 5,10,15,20- Tetraphenyl-21H, 23H-porphine nickel (II), 5,10,15,20-tetraphenyl-21H, 23H-porphine vanadium (IV) oxide, 5,10,15,20-tetra (4-pyridyl)- 21H, 23H-porphine, 29H, 31H-tetrabenzo [b, g, l, q] porphine, 2 H, 31H-tetrabenzo [b, g, l, q] porphine cobalt (II), 29H, 31H-tetrabenzo [b, g, l, q] porphine copper (II), 29H, 31H-tetrabenzo [b, g, l, q] porphine zinc (II), 29H, 31H-tetrabenzo [b, g, l, q] porphine nickel (II) or 29H, 31H-tetrabenzo [b, g, l, q] porphine vanadium (IV) oxide And preferably 5,10,15,20-tetraphenyl-21H, 23H-porphine or 29H, 31H-tetrabenzo [b, g, l, q] porphine. In addition, the above kind of compound or a mixture of plural kinds of compounds may be used.

As a method for forming a low molecular organic semiconductor compound, there are a method of forming a film by vapor deposition and a method of forming a film by converting a low molecular organic semiconductor compound precursor into a low molecular organic semiconductor compound after coating. The latter is preferred because of the process advantage that coating can be formed.
A low molecular organic semiconductor compound precursor is a substance that changes its chemical structure and is converted into a low molecular organic semiconductor compound by applying an external stimulus such as heating or light irradiation. The low molecular weight organic semiconductor compound precursor according to the present invention is preferably excellent in film formability. In particular, in order to be able to apply the coating method, it is preferable that the precursor itself can be applied in a liquid state, or the precursor is highly soluble in some solvent and can be applied as a solution. For this reason, the solubility with respect to the solvent of a low molecular organic-semiconductor compound precursor is usually 0.1 weight% or more, Preferably it is 0.5 weight% or more, More preferably, it is 1 weight% or more. On the other hand, the upper limit is not particularly limited, but is usually 50% by weight or less, preferably 40% by weight or less.

  The type of the solvent is not particularly limited as long as it can uniformly dissolve or disperse the semiconductor precursor compound. For example, aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane or decane; toluene, xylene , Aromatic hydrocarbons such as cyclohexylbenzene, chlorobenzene or orthodichlorobenzene; lower alcohols such as methanol, ethanol or propanol; ketones such as acetone, methyl ethyl ketone, cyclopentanone or cyclohexanone; ethyl acetate, butyl acetate or methyl lactate Esters such as: Chloroform, methylene chloride, dichloroethane, trichloroethane, trichloroethylene, and other halogen hydrocarbons; Ethyl ether, tetrahydrofuran, dioxane, and other ethers; Dimethyl Formamide or amides such as dimethylacetamide and the like. Of these, aromatic hydrocarbons such as toluene, xylene, cyclohexylbenzene, chlorobenzene, or orthodichlorobenzene; ketones such as acetone, methyl ethyl ketone, cyclopentanone, or cyclohexanone; chloroform, methylene chloride, dichloroethane, trichloroethane, or trichloroethylene Halogen hydrocarbons; ethers such as ethyl ether, tetrahydrofuran or dioxane. More preferably, non-halogen aromatic hydrocarbons such as toluene, xylene or cyclohexylbenzene; non-halogen ketones such as cyclopentanone or cyclohexanone; non-halogen aliphatic ethers such as tetrahydrofuran or 1,4-dioxane is there. Particularly preferred are non-halogen aromatic hydrocarbons such as toluene, xylene or cyclohexylbenzene. In addition, a solvent may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Furthermore, it is preferable that the low molecular organic semiconductor compound precursor can be easily converted into a semiconductor compound. Although what kind of external stimulus is given to the semiconductor precursor in the conversion step from the low-molecular organic semiconductor compound precursor to the semiconductor compound is arbitrary, usually heat treatment, light treatment, etc. are performed. Preferably, it is heat treatment. In this case, it is preferable that a part of the skeleton of the low molecular organic semiconductor compound precursor has a solvophilic group with respect to a predetermined solvent that can be eliminated by a reverse Diels-Alder reaction.

  Moreover, it is preferable that a low molecular organic-semiconductor compound precursor is converted into a semiconductor compound with a high yield through a conversion process. At this time, the yield of the semiconductor compound obtained by conversion from the low molecular organic semiconductor compound precursor is arbitrary as long as the performance of the organic photoelectric conversion element is not impaired, but the low molecular organic obtained from the precursor of the low molecular organic semiconductor compound The yield of the semiconductor compound is usually 90 mol% or more, preferably 95 mol% or more, more preferably 99 mol% or more.

  The low molecular organic semiconductor compound precursor is not particularly limited as long as it has the above characteristics, and specifically, compounds described in JP-A-2007-324587 and the like can be used. Particularly preferred examples include compounds represented by the following formula (A1).

In the formula (A1), at least one of X ¹ and X ² represents a group that forms a π-conjugated divalent aromatic ring, Z ¹ -Z ² is a group that can be removed by heat or light, The π-conjugated compound obtained by elimination of Z ¹ -Z ² represents a pigment molecule. X ¹ and X ² which are not a group that forms a π-conjugated divalent aromatic ring represent a substituted or unsubstituted ethenylene group.

In the compound represented by the formula (A1), Z ¹ -Z ² is eliminated by heat or light as shown in the following chemical reaction formula, and a π-conjugated compound having high planarity is generated. This produced π-conjugated compound is a semiconductor compound according to the present invention. In the present invention, the semiconductor compound preferably exhibits semiconductor characteristics.

  Examples of the compound represented by the formula (A1) include the following. T-Bu represents a t-butyl group. M represents an atomic group in which a divalent metal atom or a trivalent or higher metal is bonded to another atom.

As a method for converting the low molecular organic semiconductor compound precursor into the semiconductor compound, a known method can be used.
The low molecular organic semiconductor compound precursor represented by the formula (A1) may have a structure in which positional isomers exist, and in that case, may consist of a mixture of a plurality of positional isomers. A low-molecular organic semiconductor compound precursor composed of a plurality of positional isomers is preferable because it has a higher solubility in a solvent than a low-molecular organic semiconductor compound precursor composed of a single isomer component, so that coating film formation is easy. The reason why the solubility is improved when a mixture of multiple positional isomers is used is that the detailed mechanism is not clear, but the crystallinity of the compound itself is potentially retained, but the mixture of multiple isomers is mixed in the solution. Therefore, it is assumed that the three-dimensional regular intermolecular interaction becomes difficult. In the present invention, the solubility of the precursor mixture composed of a plurality of isomeric compounds in a non-halogen solvent is usually 0.1% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more. Although there is no restriction | limiting in an upper limit, Usually, it is 50 weight% or less, More preferably, it is 40 weight% or less.

  The p-type semiconductor compound that can be used in combination with the copolymer of the present invention is preferably a conjugated copolymer semiconductor such as polythiophene as the high molecular organic semiconductor compound, and a condensation of naphthacene, pentacene, pyrene or the like as the low molecular organic semiconductor compound. An aromatic hydrocarbon, a phthalocyanine compound and a metal complex thereof, or a porphyrin compound such as tetrabenzoporphyrin (BP) and a metal complex thereof. In addition, the above kind of compound or a mixture of plural kinds of compounds may be used.

  Although there is no special restriction | limiting about the p-type semiconductor compound layer preparation method using the organic-semiconductor material of this invention, The application | coating method is preferable. Since the copolymer of the present invention is easily soluble in a solvent, the coating film-forming property is excellent. The coating method can be performed by any of the following methods. Examples thereof include reverse roll coating, gravure coating, kiss coating, roll brushing, spray coating, air knife coating, wire barber coating, pipe doctor method, impregnation / coating method, and curtain coating method.

The high-molecular organic semiconductor compound and / or the low-molecular organic semiconductor compound may have some self-organized structure in the film-formed state, or may be in an amorphous state.
The HOMO level of the p-type semiconductor compound is not particularly limited, but can be selected depending on the type of the n-type semiconductor described later, but the HOMO level of the p-type semiconductor combined with the fullerene compound is usually −5.7 eV or more, More preferably, it is −5.5 eV or more, and usually −4.6 eV or less and −4.8 eV or less. When the HOMO level of the p-type semiconductor compound is −5.7 eV or more, the characteristics as the p-type semiconductor are improved, and when the HOMO level of the p-type semiconductor is −4.6 eV or less, the stability of the compound is improved. The open circuit voltage (Voc) is also improved. Further, the LUMO level of the p-type semiconductor is not particularly limited, but can be selected depending on the type of the n-type semiconductor described later. The LUMO level of the p-type semiconductor combined with the fullerene compound is usually −3.7 eV or more. , Preferably −3.6 eV or more. On the other hand, it is usually −2.5 eV or less, preferably −2.7 eV or less. When the LUMO level of the p-type semiconductor is −2.5 eV or less, the band gap is adjusted, light energy having a long wavelength can be effectively absorbed, and the short-circuit current density is improved. When the LUMO level of the p-type semiconductor is −3.7 eV or more, electron transfer to the n-type semiconductor easily occurs and the short-circuit current density is improved.

<N-type semiconductor compound>
The n-type semiconductor compound is not particularly limited. Specifically, it is a fullerene compound, a quinolinol derivative metal complex represented by 8-hydroxyquinoline aluminum; a condensed ring such as naphthalenetetracarboxylic acid diimide or perylenetetracarboxylic acid diimide. Tetracarboxylic acid diimides; perylene diimide derivatives, terpyridine metal complexes, tropolone metal complexes, flavonol metal complexes, perinone derivatives, benzimidazole derivatives, benzoxazole derivatives, thiazole derivatives, benzthiazole derivatives, benzothiadiazole derivatives, oxadiazole derivatives, thiadiazoles Derivatives, triazole derivatives, aldazine derivatives, bisstyryl derivatives, pyrazine derivatives, phenanthroline derivatives, quinoxaline derivatives, benzoquinoline derivatives Bipyridine derivatives, borane derivatives, anthracene, pyrene, total fluoride condensed polycyclic aromatic hydrocarbons such as naphthacene or pentacene; single-walled carbon nanotubes, n-type polymers.

  Among them, fullerene compounds, borane derivatives, thiazole derivatives, benzothiazole derivatives, benzothiadiazole derivatives, N-alkyl-substituted naphthalene tetracarboxylic acid diimides and N-alkyl-substituted perylene diimide derivatives are preferable, fullerene compounds, N-alkyl More preferred are substituted perylene diimide derivatives, N-alkyl substituted naphthalene tetracarboxylic acid diimides or n-type polymers. One or more of these compounds may be included, and one or more of n-type polymers may be included.

  Hereinafter, these preferable n-type semiconductor compounds will be described.

<Fullerene compound>
The fullerene compound of the present invention preferably has a partial structure represented by general formulas (n1), (n2), (n3) and (n4).

In the formula, FLN represents fullerene which is a carbon cluster having a closed shell structure. The carbon number of fullerene is not particularly limited as long as it is usually an even number of 60 to 130. Examples of fullerenes include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C ₈₄ , C ₉₀ , C ₉₄ , C ₉₆ and higher carbon clusters having more carbon than these. . Among these, _C60 or _C70 is preferable. As fullerenes, carbon-carbon bonds on some fullerene rings may be broken. Some carbon atoms may be replaced with other atoms. Furthermore, a metal atom, a non-metal atom, or an atomic group composed of these may be included in the fullerene cage.

a, b, c and d are integers, and the sum of a, b, c and d is usually 1 or more, and usually 5 or less, preferably 3 or less. The partial structures in (n1), (n2), (n3) and (n4) are added to the same 5-membered ring or 6-membered ring in the fullerene skeleton. In the general formula (n1), —R ⁶ and — (CH ₂ ) _L are respectively added to two adjacent carbon atoms on the same 5-membered ring or 6-membered ring in the fullerene skeleton. In the general formula (n2), -C (R ¹⁰ ) (R ¹¹ ) -N (R ¹² ) -C with respect to two adjacent carbon atoms on the same 5-membered ring or 6-membered ring in the fullerene skeleton. (R ¹³ ) (R ¹⁴ ) is added to form a 5-membered ring. In the general formula (n3), —C (R ¹⁵ ) (R ¹⁶ ) —C—C—C (R) with respect to two adjacent carbon atoms on the same 5-membered ring or 6-membered ring in the fullerene skeleton. ¹⁷ ) (R ¹⁸ ) is added to form a 6-membered ring. In the general formula (n4), —C (R ¹⁹ ) (R ²⁰ ) is added to two adjacent carbon atoms on the same 5-membered ring or 6-membered ring in the fullerene skeleton to form a 3-membered ring. It becomes. L is an integer of 1-8. L is preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

R ⁶ in the general formula (n1) has an optionally substituted alkyl group having 1 to 14 carbon atoms, an optionally substituted alkoxy group having 1 to 14 carbon atoms, or a substituent. An aromatic group that may be used.
As an alkyl group, a C1-C10 alkyl group is preferable, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, or an isobutyl group is more preferable, and a methyl group or an ethyl group is still more preferable.

As an alkoxy group, a C1-C10 alkoxy group is preferable, a C1-C6 alkoxy group is more preferable, and a methoxy group or an ethoxy group is especially preferable.
As an aromatic group, a C6-C20 aromatic hydrocarbon group or a C2-C20 aromatic heterocyclic group is preferable, a phenyl group, a thienyl group, a furyl group, or a pyridyl group is more preferable, a phenyl group or More preferred is a thienyl group.

  The substituent that the alkyl group, alkoxy group and aromatic group may have is preferably a halogen atom or a silyl group. As the halogen atom, a fluorine atom is preferable. The silyl group is preferably a diarylalkylsilyl group, a dialkylarylsilyl group, a triarylsilyl group or a trialkylsilyl group, more preferably a dialkylarylsilyl group, and even more preferably a dimethylarylsilyl group.

R ^{7 to} R ⁹ in the general formula (n1) each independently represent a substituent, which has a hydrogen atom, an alkyl group having 1 to 14 carbon atoms which may have a substituent, or a substituent. It is also a good aromatic group.
As an alkyl group, a C1-C10 alkyl group is preferable and a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, or n-hexyl group is preferable. The substituent that the alkyl group may have is preferably a halogen atom. As the halogen atom, a fluorine atom is preferable. The alkyl group substituted with a fluorine atom is preferably a perfluorooctyl group, a perfluorohexyl group or a perfluorobutyl group.

  The aromatic group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 2 to 20 carbon atoms, more preferably a phenyl group, a thienyl group, a furyl group or a pyridyl group, and a phenyl group or a thienyl group. Groups are more preferred. Examples of the substituent that the aromatic group may have include a fluorine atom, an alkyl group having 1 to 14 carbon atoms, a fluorinated alkyl group having 1 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or 3 carbon atoms. Is preferably a fluorine atom or an alkoxy group having 1 to 14 carbon atoms, more preferably a methoxy group, an n-butoxy group or a 2-ethylhexyloxy group. When the aromatic group has a substituent, the number is not limited, but is preferably 1 or more and 3 or less, and more preferably 1. When the aromatic group has a plurality of substituents, the types of the substituents may be different, but are preferably the same.

R ^{10 to} R ¹⁴ in the general formula (n2) are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 14 carbon atoms, or an optionally substituted aromatic group. It is. The alkyl group is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group or octyl group, and more preferably a methyl group. The aromatic group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 2 to 20 carbon atoms, more preferably a phenyl group or a pyridyl group, and further preferably a phenyl group.

The substituent that the alkyl group may have is preferably a halogen atom. As the halogen atom, a fluorine atom is preferable. The alkyl group substituted with a fluorine atom is preferably a perfluorooctyl group, a perfluorohexyl group or a perfluorobutyl group.
The substituent that the aromatic group may have is not particularly limited, but is preferably a fluorine atom, an alkyl group having 1 to 14 carbon atoms, or an alkoxy group having 1 to 14 carbon atoms. The alkyl group may be substituted with a fluorine atom. More preferably, it is a C1-C14 alkoxy group, More preferably, it is a methoxy group. When it has a substituent, there is no limitation in the number, However, Preferably it is 1-3, More preferably, it is 1. The types of substituents may be different but are preferably the same.

Ar ¹ in the general formula (n3) is an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 2 to 20 carbon atoms, preferably a phenyl group, A naphthyl group, a biphenyl group, a thienyl group, a furyl group, a pyridyl group, a pyrimidyl group, a quinolyl group or a quinoxalyl group, more preferably a phenyl group, a thienyl group or a furyl group. There are no limitations on the substituents that may be present, but there are no limitations on the substituents that may be present, but the substituent may be substituted with a fluorine atom, a chlorine atom, a hydroxyl group, a cyano group, a silyl group, a boryl group, or an alkyl group. May be an amino group, an alkyl group having 1 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, an alkylcarbonyl group having 1 to 14 carbon atoms, an alkylthio group having 1 to 14 carbon atoms, an alkenyl having 1 to 14 carbon atoms Group, an alkynyl group having 1 to 14 carbon atoms, an ester group, an arylcarbonyl group, an arylthio group, an aryloxy group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, preferably fluorine An atom, an alkyl group having 1 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, an ester group, an alkylcarbonyl group having 1 to 14 carbon atoms, or an arylcarbonyl group is more preferable. The alkyl group having 1 to 14 carbon atoms may be substituted with fluorine.

As the alkyl group having 1 to 14 carbon atoms, a methyl group, an ethyl group or a propyl group is preferable. As a C1-C14 alkoxy group, a methoxy group, an ethoxy group, or a propoxyl group is preferable. As the alkylcarbonyl group having 1 to 14 carbon atoms, an acetyl group is preferable.
As the ester group, a methyl ester group or an n-butyl ester group is preferable. As the arylcarbonyl group, a benzoyl group is preferable.

When it has a substituent, although there is no limitation in the number, 1-4 are preferable and 1-3 are more preferable. When there are a plurality of substituents, the types may be different, but are preferably the same.
R ^{15 to} R ¹⁸ in the general formula (n3) each independently have a hydrogen atom, an alkyl group which may have a substituent, an amino group which may have a substituent, or a substituent. It is an optionally substituted alkoxy group or an optionally substituted alkylthio group. R ¹⁵ or R ¹⁶ may form a ring with either one of R ¹⁷ or R ¹⁸ . The structure in the case of forming a ring can be represented by, for example, the general formula (n5) which is a bicyclo structure in which an aromatic group is condensed. F in the general formula (n5) is the same as c, and X is an oxygen atom, a sulfur atom, an amino group, an alkylene group, or an arylene group. The alkylene group preferably has 1 to 2 carbon atoms. As an arylene group, C5-C12 is preferable, for example, is a phenylene group. The amino group may be substituted with an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group.

The alkylene group is an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic complex having 2 to 20 carbon atoms. It may be substituted with a cyclic group.
The arylene group is an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic complex having 2 to 20 carbon atoms. It may be substituted with a cyclic group.

R ^{19 to} R ²⁰ in the general formula (n4) each independently have a hydrogen atom, an alkoxycarbonyl group, an optionally substituted alkyl group having 1 to 14 carbon atoms or a substituent. It is also a good aromatic group.
The alkoxy group in the alkoxycarbonyl group is preferably an alkoxy group having 1 to 12 carbon atoms or a fluorinated alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, a methoxy group, an ethoxy group, n -Propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, n-hexoxy group, octoxy group, 2-propylpentoxy group, 2-ethylhexoxy group, cyclohexylmethoxy group or benzyloxy group are more preferable, methoxy group, An ethoxy group, isopropoxy group, n-butoxy group, isobutoxy group or n-hexoxy group is particularly preferred.

  As the alkyl group, a linear alkyl group having 1 to 8 carbon atoms is preferable, and an n-propyl group is more preferable. The substituent that the alkyl group may have is not particularly limited, but is preferably an alkoxycarbonyl group. The alkoxy group of the alkoxycarbonyl group is preferably an alkoxy group having 1 to 14 carbon atoms or a fluorinated alkoxy group, more preferably a hydrocarbon group having 1 to 14 carbon atoms, a methoxy group, an ethoxy group, an n-propoxy group, an iso group. Propoxy group, n-butoxy group, isobutoxy group, n-hexoxy group, octoxy group, 2-propylpentoxy group, 2-ethylhexoxy group, cyclohexylmethoxy group or benzyloxy group are more preferable, and methoxy group or n-butoxy group is more preferable. Particularly preferred.

  As the aromatic group, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 2 to 20 carbon atoms is preferable, and a phenyl group, a biphenyl group, a thienyl group, a furyl group, or a pyridyl group is preferable. A group or a thienyl group is more preferred. The substituent that the aromatic group may have is preferably an alkyl group having 1 to 14 carbon atoms, a fluorinated alkyl group having 1 to 14 carbon atoms, or an alkoxy group having 1 to 14 carbon atoms, 14 alkoxy groups are more preferable, and a methoxy group or 2-ethylhexyloxy group is particularly preferable. When it has a substituent, the number is not limited, but it is preferably 1 or more and 3 or less, more preferably 1. The types of substituents may be different or the same, preferably the same.

As the structure of the general formula (n4), R ¹⁹ and R ²⁰ are preferably both alkoxycarbonyl groups, R ¹⁹ and R ²⁰ are both aromatic groups, or R ¹⁹ is an aromatic group and R ²⁰ is 3- (alkoxycarbonyl) propyl group.
The n-type semiconductor compound used in the present invention may be a single compound or a mixture of multiple compounds.

  In order for the fullerene compound to be applicable to a coating method, the fullerene compound itself may be applied in a liquid state, or the fullerene compound may be applied as a solution with high solubility in some solvent. preferable. As a preferable range of solubility, the solubility in toluene at 25 ° C. is usually 0.1% by weight or more, preferably 0.4% by weight or more, more preferably 0.7% by weight or more. It is preferable that the solubility of the fullerene compound is 0.1% by weight or more because the dispersion stability of the fullerene compound is increased and aggregation, sedimentation, separation, and the like are less likely to occur.

The solvent for the fullerene compound of the present invention is not particularly limited as long as it is a nonpolar organic solvent, but a non-halogen solvent is preferred. Although halogen-based solvents such as dichlorobenzene are also possible, alternatives are required in terms of environmental impact.
Examples of non-halogen solvents include non-halogen aromatic hydrocarbons. Of these, toluene, xylene, cyclohexylbenzene and the like are preferable.

<Method for producing fullerene compound>
Although there is no restriction | limiting in particular as a manufacturing method of the fullerene compound of this invention, For example, as a synthesis method of the fullerene compound which has a partial structure (n1), international publication 2008/059771 pamphlet, J. Org. Am. Chem. Soc. , 2008, 130 (46), 15429-15436.

As a method for synthesizing a fullerene compound having a partial structure (n2), J. et al. Am. Chem. Soc. 1993, 115, 9798-9799, Chem. Mater. 2007, 19, 5363-5372 and Chem. Mater. It can be implemented by publicly known literatures described in 2007, 19, 5194-5199.
As a synthesis method of a fullerene compound having a partial structure (n3), Angew. Chem. Int. Ed. Engl. 1993, 32, 78-80, Tetrahedron Lett. 1997, 38, 285-288, International Publication No. 2008/018931 and International Publication No. 2009/086212 can be implemented.

  As a method for synthesizing a fullerene compound having a partial structure (n4), J. et al. Chem. Soc. Perkin Trans. 1, 1997 1595, Thin Solid Films 489 (2005) 251-256, Adv. Funct. Mater. 2005, 15, 1979-1987 and J. Org. Org. Chem. It can be carried out according to known documents described in 1995, 60, 532-538.

  As commercially available fullerene compounds, for example, PCBM (manufactured by Frontier Carbon Co.), PCBNB (Frontier Carbon Co., Ltd.) and the like can be suitably used.

<N-alkyl-substituted perylene diimide derivatives>
The N-alkyl-substituted perylene diimide derivative according to the present invention is not particularly limited, and specifically, International Publication No. 2008/063609, International Publication No. 2009/115513, International Publication No. 2009/098250, Examples thereof include the compounds described in International Publication No. 2009/000756 and International Publication No. 2009/091670. High electron mobility and absorption in the visible range are preferable because they contribute to both charge transport and power generation.

<Naphthalene tetracarboxylic acid diimide>
The naphthalene tetracarboxylic acid diimide according to the present invention is not particularly limited, but specifically described in International Publication No. 2008/063609, International Publication No. 2007/146250 and International Publication No. 2009/000756. Compounds. It is preferable from the viewpoint of high electron mobility, high solubility, and excellent coating properties.

<N-type polymer>
The n-type polymer according to the present invention is not particularly limited, but condensed ring tetracarboxylic acid diimides such as naphthalene tetracarboxylic acid diimide and perylene tetracarboxylic acid diimide, perylene diimide derivatives, benzimidazole derivatives, benzoxazole derivatives, thiazoles Derivatives, benzothiazole derivatives, benzothiadiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazine derivatives, phenanthroline derivatives, quinoxaline derivatives, bipyridine derivatives, and borane derivatives include n-type polymers. It is done.

  Among them, a polymer having at least one of a borane derivative, a thiazole derivative, a benzothiazole derivative, a benzothiadiazole derivative, an N-alkyl-substituted naphthalenetetracarboxylic acid diimide and an N-alkyl-substituted perylene diimide derivative as a constituent unit is provided. Preferably, an n-type polymer having at least one of N-alkyl-substituted perylene diimide derivative and N-alkyl-substituted naphthalene tetracarboxylic acid diimide as a constituent unit is more preferable. You may contain 1 type, or 2 or more types of these compounds.

  Specific examples thereof include compounds described in International Publication No. 2009/098253, International Publication No. 2009/098250, International Publication No. 2010/012710, and International Publication No. 2009/098250. Since it has absorption in the visible region, it is preferable from the viewpoint of contributing to power generation, high viscosity, and excellent coating properties. The value of the lowest unoccupied molecular orbital (LUMO) of the n-type semiconductor is not particularly limited. For example, the value for the vacuum level calculated by the cyclic voltammogram measurement method is usually −3.85 eV or more, preferably −3. 80 eV or more. In order to efficiently move electrons from the electron donor layer (p-type semiconductor layer) to the electron acceptor layer (n-type semiconductor layer), the minimum vacancy of the materials used for each electron donor layer and electron acceptor layer is required. The relative relationship of the orbit (LUMO) is important. Specifically, the LUMO of the material of the electron donor layer is higher than the LUMO of the material of the electron acceptor layer by a predetermined energy, in other words, the electron affinity of the electron acceptor is higher than the electron affinity of the electron donor. It is preferable that the energy is larger by a predetermined energy. Since the open circuit voltage (Voc) is determined by the difference between the highest occupied orbit (HOMO) of the electron donor layer material and the LUMO of the electron acceptor layer material, increasing the LUMO of the electron acceptor increases the Voc. Tend. On the other hand, the LUMO value is usually −1.0 eV or less, preferably −2.0 eV or less, more preferably −3.0 eV or less, and still more preferably −3.3 eV or less. Lowering the LUMO of the electron acceptor tends to cause electron migration and increase the short-circuit current (Jsc).

  As a method for calculating the value of LUMO of an n-type semiconductor compound, there are a method of theoretically obtaining a calculated value and a method of actually measuring. Theoretically calculated methods include semi-empirical molecular orbital methods and non-empirical molecular orbital methods. Examples of the actual measurement method include ultraviolet-visible absorption spectrum measurement method and cyclic voltammogram measurement method. Among them, the cyclic voltammogram measurement method is preferable. Specifically, it can measure by the method as described in well-known literature (International publication 2011/016430), for example.

  Although the HOMO value of the n-type semiconductor compound is not particularly limited, it is usually −5.0 eV or less, preferably −5.5 eV or less. On the other hand, it is usually −7.0 eV or more, preferably −6.6 eV or more. The n-type semiconductor compound having a HOMO value of −7.0 eV or more is preferable in that the absorption of the n-type material can also be used for power generation. It is preferable that the HOMO value of the n-type semiconductor compound is −5.0 eV or less in that the reverse movement of holes can be prevented.

The electron mobility of the n-type semiconductor compound is not particularly limited, but is usually 1.0 × 10 ⁻⁶ cm ² / Vs or more, preferably 1.0 × 10 ⁻⁵ cm ² / Vs or more. 0 × 10 ⁻⁵ cm ² / Vs or more is more preferable, and 1.0 × 10 ⁻⁴ cm ² / Vs or more is more preferable. On the other hand, it is usually 1.0 × 10 ³ cm ² / Vs or less, preferably 1.0 × 10 ² cm ² / Vs or less, and more preferably 5.0 × 10 ¹ cm ² / Vs or less. When the electron mobility of the compound is 1.0 × 10 ⁻⁶ cm ² / Vs or more, effects such as improvement of the electron diffusion rate, improvement of short circuit current, and improvement of conversion efficiency of the photoelectric conversion element tend to increase. Therefore, it is preferable.

  An example of the measurement method is an FET method, which can be performed by a method described in a known document (Japanese Patent Application Laid-Open No. 2010-045186).

  The solubility of the n-type semiconductor compound in toluene at 25 ° C. is usually 0.5% by weight or more, preferably 0.6% by weight or more, and more preferably 0.7% by weight or more. On the other hand, it is usually preferably 90% by weight or less, more preferably 80% by weight or less, and further preferably 70% by weight or less. By setting the solubility of the compound in toluene at 25 ° C. to 0.5% by weight or more, the dispersion stability of the n-type semiconductor material in the solvent is improved, and aggregation, sedimentation, separation, and the like are less likely to occur. preferable.

<Buffer layer (102, 104)>
The photoelectric conversion element 107 of the present invention preferably further includes one or more buffer layers in addition to the pair of electrodes (101, 105) and the organic active layer 103 disposed therebetween. The buffer layer can be classified into an electron extraction layer 104 and a hole extraction layer 102, and can be provided between the organic active layer 103 and the electrodes (101, 105), respectively. By providing the buffer layer, there are advantages that the mobility of electrons and holes between the active layer and the electrode is increased, and that a short circuit between the electrodes can be prevented.
The electron extraction layer 104 and the hole extraction layer 102 are disposed so as to sandwich the organic active layer 103 between a pair of electrodes (101, 105). That is, when the photoelectric conversion element 107 according to the present invention includes both the electron extraction layer 104 and the hole extraction layer 102, the electrode 101, the hole extraction layer 102, the organic active layer 103, the electron extraction layer 104, and the electrode 105 Arranged in order. When the photoelectric conversion element 107 according to the present invention includes the electron extraction layer 104 and does not include the hole extraction layer 102, the electrode 101, the organic active layer 103, the electron extraction layer 104, and the electrode 105 are arranged in this order. The stacking order of the electron extraction layer 104 and the hole extraction layer 102 may be reversed, or at least one of the electron extraction layer 104 and the hole extraction layer 102 may be composed of a plurality of different films. .

<Electron extraction layer 104>
The material of the electron extraction layer 104 is not particularly limited as long as it can improve the efficiency of extracting electrons from the organic active layer 103 containing the p semiconductor compound and the n semiconductor compound to the electrode 101. Specifically, an inorganic compound or an organic compound is mentioned. As the material of the inorganic compound, an alkali metal salt such as Li, Na, K, or Cs; an n-type oxide semiconductor such as titanium oxide (TiOx) or zinc oxide (ZnO) is desirable.

As the alkali metal salt, a fluoride salt such as LiF, NaF, KF or CsF is desirable. Although the operation mechanism of such a material is unknown, it is possible to reduce the work function of the cathode 105 in combination with an electron extraction electrode (cathode 105) such as Al to increase the voltage applied to the inside of the solar cell element. It is done.
Specific examples of the organic compound material include bathocuproin (BCP), bathophenanthrene (Bphen), (8-hydroxyquinolinato) aluminum (Alq3), boron compound, oxadiazole compound, benzimidazole compound, and naphthalenetetracarboxylic acid. Examples include acid anhydrides (NTCDA), perylene tetracarboxylic acid anhydrides (PTCDA), and phosphine compounds having a double bond with a Group 16 element such as a phosphine oxide compound or a phosphine sulfide compound. Among them, a phosphine compound having a double bond with a group 16 element substituted with an aryl group, such as a phosphine oxide compound substituted with an aryl group or a phosphine sulfide compound substituted with an aryl group, is more preferable. , Triarylphosphine oxide compounds, triarylphosphine sulfide compounds, aromatic hydrocarbon compounds having two or more diarylphosphine oxide units, two aromatic hydrocarbon compounds or two diarylphosphine oxide units having two or more diarylphosphine sulfide units An aromatic hydrocarbon compound having the above. The aryl group may be substituted with an alkyl group substituted with a fluorine atom such as a fluorine atom or a perfluoroalkyl group. In addition to the above materials, alkali metal or alkaline earth metal may be doped.

  The LUMO value of the material of the electron extraction layer 104 is not particularly limited, but is usually −4.0 eV or more, preferably −3.9 eV or more. On the other hand, it is usually −1.9 eV or less, preferably −2.0 eV or less. The LUMO value of the material of the electron extraction layer 104 is preferably −1.9 eV or less, which is preferable in that charge transfer is promoted. When the LUMO value of the material of the electron extraction layer 104 is −4.0 eV or more, it is preferable in that reverse electron transfer to the n-type material is prevented.

  As a method for calculating the LUMO value of the material of the electron extraction layer 104, there is a cyclic voltammogram measurement method. For example, it can implement with reference to the method as described in well-known literature (International publication 2011/016430).

  The HOMO value of the material of the electron extraction layer 104 is not particularly limited, but is usually −9.0 eV or more, preferably −8.0 eV or more. On the other hand, it is usually −5.0 eV or less, preferably −5.5 eV or less. When the HOMO value of the material of the electron extraction layer 104 is −5.0 eV or less, it is preferable in that holes can be prevented from moving.

  When the material of the electron extraction layer 104 is an organic compound, the glass transition temperature (hereinafter also referred to as Tg) of this compound by the DSC method is not particularly limited but is not observed or 55 ° C. The above is preferable. That the glass transition temperature by DSC method is not observed means that there is no glass transition temperature. Specifically, the determination is made based on the presence or absence of a glass transition temperature of 400 ° C. or lower. A material in which the glass transition temperature by the DSC method is not observed is preferable in that it has high thermal stability.

  Among compounds having a glass transition temperature by DSC of 55 ° C. or higher, a compound having a glass transition temperature of preferably 65 ° C. or higher, more preferably 80 ° C. or higher, further preferably 110 ° C. or higher, particularly preferably 120 ° C. or higher. Is desirable. On the other hand, the upper limit of the glass transition temperature is not particularly limited, but is usually 400 ° C. or lower, preferably 350 ° C. or lower, more preferably 300 ° C. or lower. The material of the electron extraction layer 104 is preferably a material whose glass transition temperature by DSC method is not observed to be 30 ° C. or higher and lower than 55 ° C.

  In the present specification, the glass transition temperature is defined as a point at which specific heat is changed in a solid state of a compound, which is a temperature at which local molecular motion is initiated by thermal energy. When the temperature rises further than Tg, the solid structure changes and crystallization occurs (the temperature at this time is defined as the crystallization temperature (Tc)). When the temperature rises further, it generally melts at the melting point (Tm) and changes to a liquid state. However, these phase transitions may not be observed due to molecular decomposition or sublimation at high temperatures. What is necessary is just to measure a glass transition temperature by a well-known method, for example, DSC method is mentioned.

  The DSC method is a thermophysical property measurement method (differential scanning calorimetry method) defined in JIS K-0129 “General Rules for Thermal Analysis”. The glass transition temperature is a temperature at which molecular motion starts from a glass state, and can be measured by DSC as a temperature at which specific heat changes. In order to determine the glass transition temperature more clearly, it is desirable to measure after rapidly cooling a sample once heated to a temperature higher than the glass transition temperature. For example, it can be carried out by the method described in known literature (International Publication No. 2011/016430).

  Since the glass transition temperature of the compound used for the electron extraction layer is 55 ° C. or higher, the structure of the compound is difficult to change with respect to external stress such as applied electric field, flowing current, stress due to bending or temperature change. Therefore, it is preferable in terms of durability. Furthermore, since there is a tendency that the crystallization of the thin film of the compound does not proceed easily, the stability of the electron extraction layer is improved by making it difficult for the compound to change between the amorphous state and the crystalline state in the operating temperature range. Therefore, it is preferable in terms of durability. This effect becomes more prominent as the glass transition temperature of the material is higher.

  The thickness of the electron extraction layer 104 is not particularly limited, but is usually 0.01 nm or more, preferably 0.1 nm or more, more preferably 0.5 nm or more. On the other hand, it is usually 40 nm or less, preferably 20 nm or less. When the film thickness of the electron extraction layer 104 is 0.01 nm or more, it functions as a buffer material. When the film thickness of the electron extraction layer 104 is 40 nm or less, electrons are easily extracted, and photoelectric conversion is performed. Efficiency is improved.

<A phosphine compound having a double bond with a Group 16 element>
As the phosphine compound having a double bond with the Group 16 element, a compound represented by the following general formula (P1) is preferable. The use of a compound represented by the following general formula (P1) as a material for the electron extraction layer 104 is preferable in that the photoelectric conversion efficiency is improved and / or the durability of the photoelectric conversion element is improved.

  In formula (P1), p represents an integer of 1 or more and is usually 6 or less, preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

R ²¹ and R ²² each independently represent a hydrocarbon group that may have a substituent, an alkoxy group that may have a substituent, or a heterocyclic group that may have a substituent. R ²¹ and R ²² may be bonded to each other to form a ring. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include saturated aliphatic hydrocarbon groups such as alkyl groups (including cycloalkyl groups); unsaturated aliphatic hydrocarbon groups such as alkenyl groups (including cycloalkenyl groups) or alkynyl groups. . Of these, a saturated aliphatic hydrocarbon group such as an alkyl group is preferable. Examples of the heterocyclic group include an aliphatic heterocyclic group and an aromatic heterocyclic group. That is, R ²¹ and R ²² may be an aromatic group (aryl group) such as an aromatic hydrocarbon group or an aromatic heterocyclic group.

Among them, at least one of R ²¹ and R ²² has a saturated aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a substituent. It is preferably an aromatic heterocyclic group. When at least one of R ²¹ and R ²² is a saturated aliphatic hydrocarbon group, solubility is improved, which is preferable in that film formation by coating is facilitated. On the other hand, it is preferable that at least one of R ²¹ and R ²² is an aromatic group in terms of improving thermal stability. Further, since the aromatic group has high planarity, it is considered that when at least one of R ²¹ and R ²² is an aromatic compound, an n-type semiconductor compound and an phosphine compound of the active layer 103 described later are likely to interact with each other. It is done. This is particularly preferred because charge transfer between the buffer layer and the active layer is more likely to occur.

When p is 2 or more, a plurality of R ²¹ and a plurality of R ²² exist, but the plurality of R ²¹ and the plurality of R ²² may be independently different from each other. Further, any two or more of the plurality of R ²¹ and the plurality of R ²² may be bonded to each other to form a ring.

  As an alkyl group, a C1-C20 thing is preferable, for example, a methyl group, an ethyl group, i-propyl group, t-butyl group, a hexyl group, etc. are mentioned.

  As a cycloalkyl group, a C3-C20 thing is preferable, for example, a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group etc. are mentioned.

  As an alkenyl group, a C2-C20 thing is preferable, for example, a vinyl group or a styryl group etc. are mentioned.

  As a cycloalkenyl group, a C3-C20 thing is preferable, for example, a cyclopropenyl group, a cyclopentenyl group, or a cyclohexenyl group etc. are mentioned.

  As the alkynyl group, those having 2 to 20 carbon atoms are preferable, and examples thereof include a methylethynyl group and a trimethylsilylethynyl group.

  As the aromatic hydrocarbon group, those having 6 to 30 carbon atoms are preferable, for example, phenyl group, naphthyl group, phenanthryl group, biphenylenyl group, triphenylenyl group, anthryl group, pyrenyl group, fluorenyl group, azulenyl group, acenaphthenyl group, Examples include a fluoranthenyl group, a naphthacenyl group, a perylenyl group, a pentacenyl group, a quarterphenyl group, and the like. Of these, a phenyl group, a naphthyl group, a phenanthryl group, a triphenylenyl group, an anthryl group, a pyrenyl group, a fluorenyl group, an acenaphthenyl group, a fluoranthenyl group, or a perylenyl group is preferable.

  As the alkoxy group, those having 2 to 20 carbon atoms are preferable. For example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group and t-butoxy group, benzyloxy And straight-chain or branched alkoxy groups such as an ethylhexyloxy group.

  As the aliphatic heterocyclic group, those having 2 to 30 carbon atoms are preferable, and examples thereof include a pyrrolidinyl group, piperidinyl group, piperazinyl group, tetrahydrofuranyl group, dioxanyl group, morpholinyl group and thiomorpholinyl group. Of these, a pyrrolidinyl group, a piperidinyl group, or a piperazinyl group is preferable. As the aromatic heterocyclic group, those having 2 to 30 carbon atoms are preferable, for example, pyridyl group, thienyl group, furyl group, pyrrolyl group, oxazolyl group, thiazolyl group, oxadiazolyl group, thiadiazolyl group, pyrazinyl group, pyrimidinyl group, Pyrazolyl group, imidazolyl group, benzothienyl group, dibenzofuryl group, dibenzothienyl group, phenylcarbazolyl, phenoxathiinyl group, xanthenyl group, benzofuranyl group, thianthenyl group, indolizinyl group, phenoxazinyl group, phenothiazinyl group, acridinyl group Phenanthridinyl group, phenanthrolinyl group, quinolyl group, isoquinolyl group, indolyl group or quinoxalinyl group. Among them, pyridyl group, pyrazinyl group, pyrimidinyl group, pyrazolyl group, quinolyl group, isoquinolyl group, imidazolyl group, acridinyl group, phenanthridinyl group, phenanthrolinyl group, quinoxalinyl group, dibenzofuryl group, dibenzothienyl group, A phenylcarbazolyl, xanthenyl group or phenoxazinyl group is preferred.

  The aromatic hydrocarbon group or aromatic heterocyclic group may be a condensed polycyclic aromatic group. The ring forming the condensed polycyclic aromatic group may have a cyclic alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a substituent. Aromatic heterocyclic groups are preferred. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group. Examples of the aromatic heterocyclic group include pyridyl group, thienyl group, furyl group, pyrrolyl group, oxazolyl group, thiazolyl group, oxadiazolyl group, thiadiazolyl group, pyrazinyl group, pyrimidinyl group, pyrazolyl group, and imidazolyl group. Among these, a pyridyl group or a thienyl group is preferable.

  Preferred examples of the condensed polycyclic aromatic group include a condensed polycyclic aromatic hydrocarbon group and a condensed polycyclic aromatic heterocyclic group. Preferable examples of the condensed polycyclic aromatic hydrocarbon group include a phenanthryl group, an anthryl group, a pyrenyl group, a fluoranthenyl group, a naphthacenyl group, a perylenyl group, a pentacenyl group, and a triphenylenyl group. In addition, preferable examples of the condensed polycyclic aromatic heterocyclic group include a phenoxazinyl group, a phenothiazinyl group, an acridinyl group, a phenanthridinyl group, and a phenanthrolinyl group.

Specific examples of the condensed polycyclic aromatic group include the following, but are not limited thereto. Further, in the following condensed polycyclic aromatic group, the position of the atom bonded to the phosphorus atom is not particularly limited.

R ²³ represents a p-valent hydrocarbon group which may have a substituent, a p-valent heterocyclic group which may have a substituent, or a hydrocarbon group which may have a substituent and a substituent. It represents a p-valent group in which at least one of the heterocyclic groups which may have a group is linked. That is, R ²³ can be an aromatic group such as an aromatic hydrocarbon group or an aromatic heterocyclic group. R ²³ may be a p-valent condensed polycyclic aromatic group which may have a substituent. R ²³ is preferably a p-valent aromatic group which may have a substituent, and more preferably a p-valent condensed polycyclic aromatic group which may have a substituent.

Examples of the hydrocarbon group include the monovalent hydrocarbon group described for R ²¹ and R ²² or the corresponding divalent to hexavalent hydrocarbon group. The types of hydrocarbon groups, likewise include aliphatic hydrocarbon group or an aromatic hydrocarbon group as R ²¹ and R ^22.

Examples of the heterocyclic group include the monovalent heterocyclic group described for R ²¹ and R ²² or the corresponding divalent to hexavalent heterocyclic group. As the type of the heterocyclic group, an aliphatic heterocyclic group or an aromatic heterocyclic group can be used in the same manner as R ²¹ and R ²² .

Examples of the condensed polycyclic aromatic group include the monovalent condensed polycyclic aromatic group described for R ²¹ and R ²² or the condensed polycyclic aromatic group having 2 to 6 valences.

When R ²³ is a divalent group, the following specific examples can be given, but the invention is not limited thereto.

The term “which may have a substituent” in the description of R ²¹ , R ²² and R ²³ means that it may have one or more substituents. This substituent is not particularly limited, but is a halogen atom, hydroxyl group, cyano group, amino group, carboxyl group, carbonyl group, acetyl group, sulfonyl group, silyl group, boryl group, nitrile group, alkyl group, alkenyl group, alkynyl. Group, alkoxy group, aromatic hydrocarbon group or aromatic heterocyclic group.

  As the halogen atom, a fluorine atom is preferable.

  As an alkyl group, a C1-C20 thing is preferable, for example, a methyl group, an ethyl group, i-propyl group, t-butyl group, a cyclohexyl group, etc. are mentioned.

  The alkenyl group preferably has 2 to 20 carbon atoms, and examples thereof include a vinyl group, a styryl group, and a diphenylvinyl group.

  As the alkynyl group, those having 2 to 20 carbon atoms are preferable, and examples thereof include a methylethynyl group, a phenylethynyl group, and a trimethylsilylethynyl group.

  As a silyl group, a C2-C20 thing is preferable, for example, a trimethylsilyl group, a triphenylsilyl group, etc. are mentioned.

  Examples of the boryl group include an aromatic group-substituted boryl group such as a dimesitylboryl group.

  As the alkoxy group, those having 2 to 20 carbon atoms are preferable. For example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, ethylhexyloxy group, benzyloxy group And linear or branched alkoxy groups such as t-butoxy group.

  Examples of the amino group include aromatic substituted amines such as a diphenylamino group, a ditolylamino group, and a carbazolyl group.

  As the aromatic hydrocarbon group, those having 6 to 20 carbon atoms are preferable, and these are not limited to monocyclic groups at all, and monocyclic aromatic hydrocarbon groups, condensed polycyclic aromatic hydrocarbon groups, and ring-linked aromatic groups. Any of hydrocarbon groups may be used.

  Examples of the monocyclic aromatic hydrocarbon group include a phenyl group. Examples of the condensed polycyclic aromatic hydrocarbon group include a biphenyl group, a phenanthryl group, a naphthyl group, an anthryl group, a fluorenyl group, a pyrenyl group, and a perylenyl group. Examples of the ring-linked aromatic hydrocarbon group include a biphenyl group and terphenyl. Among these, a phenyl group or a naphthyl group is preferable.

  As the aromatic heterocyclic group, those having 5 to 20 carbon atoms are preferable, for example, pyridyl group, thienyl group, furyl group, oxazolyl group, thiazolyl group, oxadiazolyl group, benzothienyl group, dibenzofuryl group, dibenzothienyl group, Examples include a pyrazinyl group, a pyrimidinyl group, a pyrazolyl group, an imidazolyl group, and a phenylcarbazolyl group. Among these, a pyridyl group, a thienyl group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, or a phenanthryl group is preferable.

  In the formula (P1), X represents a group 16 element, and specific examples include oxygen, sulfur, and selenium. Of these, oxygen or sulfur is preferable, and oxygen is particularly preferable. Specific examples of the compound represented by the formula (P1) (X represents a group 16 element such as oxygen, sulfur or selenium) are exemplified below.

<Hole extraction layer 102>
The material of the hole extraction layer 102 is not particularly limited as long as the hole extraction efficiency from the organic active layer 103 to the anode 101 can be improved. Specifically, conductive polymers in which polythiophene, polypyrrole, polyacetylene, triphenylenediamine, polyaniline, etc. are doped with sulfonic acid and / or iodine, polythiophene derivatives having a sulfonyl group as a substituent, conductive organic materials such as arylamine Examples thereof include compounds and p-type semiconductor compounds described later. Among them, a conductive polymer doped with sulfonic acid is preferable, and poly (3,4-ethylenedioxythiophene) poly (styrenesulfonic acid) (PEDOT: PSS) in which a polythiophene derivative is doped with polystyrene sulfonic acid is more preferable. A thin film of metal such as gold, indium, silver or palladium can also be used. Furthermore, a thin film of metal or the like may be formed alone or in combination with the above organic material.

The thickness of the hole extraction layer 102 is not particularly limited, but is usually 2 nm or more. On the other hand, it is usually 40 nm or less, preferably 20 nm or less. When the film thickness of the hole extraction layer 102 is 2 nm or more, it functions as a buffer material. When the film thickness of the hole extraction layer 102 is 40 nm or less, holes are easily extracted, Conversion efficiency is improved.
There is no limitation on the formation method of the electron extraction layer 104 and the hole extraction layer 102. For example, when a material having sublimation property is used, it can be formed by a vacuum deposition method or the like. Further, for example, when a material soluble in a solvent is used, it can be formed by a wet coating method such as spin coating or inkjet. When a semiconductor material is used for the hole extraction layer 102, the precursor may be converted into a semiconductor compound after the layer is formed using the precursor, similarly to the low-molecular organic semiconductor compound of the organic active layer described above.

<Electrodes 101, 105>
The electrodes (101 and 105) according to the present invention have a function of collecting holes and electrons generated by light absorption. Therefore, the pair of electrodes includes an electrode 101 suitable for collecting holes (hereinafter also referred to as an anode) and an electrode 105 suitable for collecting electrons (hereinafter also referred to as a cathode). Is preferably used. Any one of the pair of electrodes may be translucent, and both may be translucent. Translucency means that sunlight passes through 40% or more. In addition, it is preferable that the transparent electrode has a solar ray transmittance of 70% or more in order to allow light to reach the active layer through the transparent electrode. The light transmittance can be measured with a normal spectrophotometer.

The electrode 101 (anode) suitable for collecting holes is a conductive material generally having a work function higher than that of the cathode, and an electrode having a function of smoothly extracting holes generated in the organic active layer 103. It is.
Examples of the material of the anode 101 include conductive metal oxidation such as nickel oxide, tin oxide, indium oxide, indium tin oxide (ITO), indium-zirconium oxide (IZO), titanium oxide, indium oxide, or zinc oxide. A metal such as gold, platinum, silver, chromium or cobalt, or an alloy thereof.

  Since these substances have a high work function, they are preferable, and further, a conductive polymer material typified by PEDOT / PSS in which a polythiophene derivative is doped with polystyrene sulfonic acid can be laminated. When laminating such a conductive polymer, the work function of the conductive polymer material is high, so that it is suitable for cathodes such as Al and Mg, even if it is not a material with a high work function as described above. Metals can also be widely used.

A PEDOT / PSS in which a polythiophene derivative is doped with polystyrene sulfonic acid, or a conductive polymer material doped with iodine or the like in polypyrrole or polyaniline can also be used as the anode material.
When the anode 101 is a transparent electrode, it is preferable to use a conductive metal oxide having translucency such as ITO, zinc oxide or tin oxide, and ITO is particularly preferable.

  The film thickness of the anode 101 is not particularly limited, but is usually 10 nm or more, preferably 20 nm or more, and more preferably 50 nm or more. On the other hand, it is usually 10 μm or less, preferably 1 μm or less, more preferably 500 nm or less. When the film thickness of the anode 101 is 10 nm or more, the sheet resistance is suppressed, and when the film thickness of the anode 101 is 10 μm or less, light can be efficiently converted into electricity without decreasing the light transmittance. it can. When used for a transparent electrode, it is necessary to select a film thickness that achieves both light transmittance and sheet resistance.

The sheet resistance of the anode 101 is not particularly limited, but is usually 1Ω / □ or more, on the other hand, 1000Ω / □ or less, preferably 500Ω / □ or less, more preferably 100Ω / □ or less.
A method for forming the anode 101 includes a vacuum film formation method such as vapor deposition or sputtering, or a method of forming a film by applying an ink containing nanoparticles or a precursor.

The electrode 105 (cathode) suitable for collecting electrons is a conductive material generally having a work function higher than that of the anode, and is an electrode having a function of smoothly extracting electrons generated in the organic active layer 103. It is characterized by being adjacent to the electron extraction layer 104 of the present invention.
Examples of the material of the cathode 105 include metals such as platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, cesium, calcium, and magnesium, and alloys thereof; Examples include inorganic salts such as lithium and cesium fluoride; metal oxides such as nickel oxide, aluminum oxide, lithium oxide, and cesium oxide. These materials are preferred because they have a low work function. Similarly to the anode 101, a material having a high work function suitable for the anode 101 can be used for the cathode 105 by using an n-type semiconductor such as titania having conductivity for the electron extraction layer 104. From the viewpoint of electrode protection, the anode 101 material is preferably a metal such as platinum, gold, silver, copper, iron, tin, aluminum, calcium, or indium and an alloy using these metals.

  The film thickness of the cathode 105 is not particularly limited, but is usually 10 nm or more, preferably 20 nm or less, and more preferably 50 nm or more. On the other hand, it is usually 10 μm or less, preferably 1 μm or less, more preferably 500 nm or less. When used for a transparent electrode, it is necessary to select a film thickness that achieves both light transmittance and sheet resistance. When the film thickness of the cathode 105 is 10 nm or more, sheet resistance is suppressed, and when the film thickness of the cathode 105 is 10 μm or less, light can be efficiently converted into electricity without a decrease in light transmittance. it can.

The sheet resistance of the cathode 105 is not particularly limited, but is usually 1000Ω / □ or less, preferably 500Ω / □ or less, and more preferably 100Ω / □ or less. Although there is no restriction on the lower limit, it is usually 1Ω / □ or more.
Examples of the method for forming the cathode 105 include a vacuum film formation method such as vapor deposition or sputtering, or a method of forming a film by applying an ink containing nanoparticles or a precursor.
Further, two or more layers of the anode 101 or the cathode 105 may be stacked, and characteristics (electric characteristics, wetting characteristics, etc.) may be improved by surface treatment.

  After laminating the anode 101 and the cathode 105, the photoelectric conversion element is usually in a temperature range of 50 ° C. or higher, preferably 80 ° C. or higher, usually 300 ° C. or lower, preferably 280 ° C. or lower, more preferably 250 ° C. or lower. It is preferable to heat (this step may be referred to as an annealing treatment step). It is preferable to set the temperature of the annealing treatment step to 50 ° C. or higher because an effect of improving the adhesion between the electron extraction layer 104 and the electrode 101 and / or the electron extraction layer 104 and the active layer 103 can be obtained. It is preferable to set the temperature of the annealing treatment step to 300 ° C. or lower because the organic compound in the active layer is less likely to be thermally decomposed.

In addition, about temperature operation, you may heat in steps within the said range.
The heating time is usually 1 minute or longer, preferably 3 minutes or longer, and usually 3 hours or shorter, preferably 1 hour or shorter. The annealing process is preferably terminated when the open circuit voltage, short circuit current, and fill factor, which are parameters of the solar cell performance, reach a constant value. Further, it is preferable that the annealing treatment be performed under normal pressure and in an inert gas atmosphere.

With the annealing treatment step, by improving the adhesion between the electron extraction layer 104 and the electrode 101 and / or the electron extraction layer 104 and the active layer 103, the effect of improving the thermal stability and durability of the photoelectric conversion element, The effect of promoting the self-organization of the organic active layer is obtained.
As a method for heating, the photoelectric conversion element may be placed on a heat source such as a hot plate, or the photoelectric conversion element may be put in a heating atmosphere such as an oven. Moreover, it may be a batch type or a continuous type.

<Substrate 106>
The photoelectric conversion element according to the present invention usually has a substrate 106 that serves as a support. That is, an electrode, an active layer, and a buffer layer are formed on the substrate. The material of the substrate (substrate material) is arbitrary as long as the effects of the present invention are not significantly impaired. Preferred examples of the substrate material include inorganic materials such as quartz, glass, sapphire and titania; polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, fluorine Resin film, polyolefin such as vinyl chloride or polyethylene, cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, epoxy resin or other organic materials; paper such as paper or synthetic paper; stainless steel, Examples thereof include composite materials such as those obtained by coating or laminating a surface of a metal such as titanium or aluminum to impart insulation.

Examples of the glass include soda glass, blue plate glass, and alkali-free glass. As for the glass material, alkali-free glass is preferred because it is better that there are fewer ions eluted from the glass.
There is no restriction | limiting in the shape of the board | substrate 106, For example, shapes, such as a board, a film, a sheet | seat, can be used. There is no limitation on the film thickness of the substrate 106. However, it is usually 5 μm or more, particularly 20 μm or more. On the other hand, it is usually preferably 20 mm or less, particularly preferably 10 mm or less. It is preferable that the thickness of the substrate is 5 μm or more because the possibility that the strength of the semiconductor device is insufficient is reduced. It is preferable that the film thickness of the substrate is 20 mm or less because the cost is suppressed and the weight is not increased. When the substrate is glass, the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, while it is usually 1 cm or less, preferably 0.5 cm or less. When the film thickness of the glass substrate is 0.01 mm or more, the mechanical strength increases and it is difficult to break, which is preferable. It is preferable that the thickness of the glass substrate is 0.5 cm or less without increasing the weight.

<Solar cell module>
[Solar cell module 13]
The photoelectric conversion element 107 of the present invention is preferably used as a thin film solar cell as a solar cell element.
FIG. 2 is a cross-sectional view schematically showing the configuration of a thin film solar cell as one embodiment of the present invention. As shown in FIG. 2, the thin film solar cell 14 of this embodiment includes a weather-resistant protective film 1, an ultraviolet cut film 2, a gas barrier film 3, a getter material film 4, a sealing material 5, and a solar cell element. 6, a sealing material 7, a getter material film 8, a gas barrier film 9, and a back sheet 10 are provided in this order. And light is irradiated from the side (downward in the figure) where the weather-resistant protective film 1 is formed, and the solar cell element 6 generates power. In addition, when using a highly waterproof sheet such as a sheet in which a fluororesin film is bonded to both surfaces of an aluminum foil as the back sheet 10 described later, the getter material film 8 and / or the gas barrier film 9 may not be used depending on the application. Good.

[Weather-resistant protective film 1]
The weather-resistant protective film 1 is a film that protects the solar cell element 6 from weather changes.
Some components of the solar cell element 6 are deteriorated by temperature change, humidity change, natural light, and / or erosion caused by wind and rain. Therefore, by covering the solar cell element 6 with the weather-resistant protective film 1, the solar cell element 6 and the like are protected from weather changes and the like, and the power generation capacity is kept high.

Since the weather resistant protective film 1 is located on the outermost layer of the thin film solar cell 14, the surface covering material of the thin film solar cell 14 such as weather resistance, heat resistance, transparency, water repellency, stain resistance and / or mechanical strength is provided. It is preferable to have a property suitable for the above and to maintain it for a long period of time in outdoor exposure.
Moreover, the weather-resistant protective film 1 is preferably one that transmits visible light from the viewpoint of not preventing the solar cell element 6 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is preferably 80% or more, more preferably 90% or more, and particularly preferably 95%.

  Furthermore, since the thin-film solar cell 14 is often heated by receiving light, it is preferable that the weather-resistant protective film 1 also has heat resistance. From this viewpoint, the melting point of the constituent material of the weather-resistant protective film 1 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower. Preferably it is 300 degrees C or less. By increasing the melting point, it is possible to reduce the possibility that the weather resistant protective film 1 is melted and deteriorated when the thin film solar cell 14 is used.

  The material which comprises the weather-resistant protective film 1 is arbitrary as long as it can protect the solar cell element 6 from a weather change. Examples of the material include polyethylene resin, polypropylene resin, cyclic polyolefin resin, AS (acrylonitrile-styrene) resin, ABS (acrylonitrile-butadiene-styrene) resin, polyvinyl chloride resin, fluorine resin, polyethylene terephthalate, polyethylene Examples thereof include polyester resins such as naphthalate, phenol resins, polyacrylic resins, polyamide resins such as various nylons, polyimide resins, polyamide-imide resins, polyurethane resins, cellulose resins, silicone resins, and polycarbonate resins.

  Among them, fluorine resin is preferable, and specific examples thereof include polytetrafluoroethylene (PTFE), 4-fluoroethylene-perchloroalkoxy copolymer (PFA), 4-fluoroethylene-6-fluoride. Propylene copolymer (FEP), 2-ethylene-4-fluoroethylene copolymer (ETFE), poly-3-fluoroethylene chloride (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), etc. Can be mentioned.

In addition, the weather-resistant protective film 1 may be formed with 1 type of material, and may be formed with 2 or more types of materials. Moreover, although the weather-resistant protective film 1 may be formed with the single layer film, the laminated | multilayer film provided with the film of 2 or more layers may be sufficient as it.
The thickness of the weather-resistant protective film 1 is not particularly specified, but is usually 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and usually 200 μm or less, preferably 180 μm or less, more preferably 150 μm or less. Increasing the thickness tends to increase mechanical strength, and decreasing the thickness tends to increase flexibility.

Moreover, you may perform surface treatments, such as a corona treatment and / or a plasma treatment, for the weather-resistant protective film 1 in order to improve adhesiveness with another film.
The weatherproof protective film 1 is preferably provided on the outer side as much as possible in the thin-film solar cell 14. This is because more of the constituent members of the thin-film solar cell 14 can be protected.

[UV cut film 2]
The ultraviolet cut film 2 is a film that prevents the transmission of ultraviolet rays.
Some components of the thin film solar cell 14 are deteriorated by ultraviolet rays. Some of the gas barrier films 3, 9 and the like are deteriorated by ultraviolet rays depending on the type. Therefore, the ultraviolet cut film 2 is provided in the light receiving portion of the thin-film solar cell 14, and the ultraviolet cut film 2 covers the light receiving surface 6a of the solar cell element 6, whereby the solar cell element 6 and, if necessary, the gas barrier films 3, 9 and the like. Can be protected from ultraviolet rays and the power generation capacity can be kept high.

The degree of the ability to suppress the transmission of ultraviolet rays required for the ultraviolet cut film 2 is such that the transmittance of ultraviolet rays (for example, wavelength 300 nm) is preferably 50% or less, more preferably 30% or less, and particularly preferably. 10% or less.
Further, the ultraviolet cut film 2 is preferably one that transmits visible light from the viewpoint of not preventing the solar cell element 6 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more.

  Furthermore, since the thin film solar cell 14 is often heated by receiving light, the ultraviolet cut film 2 preferably has heat resistance. From this viewpoint, the melting point of the constituent material of the ultraviolet cut film 2 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably. Is 300 ° C. or lower. If the melting point is too low, the ultraviolet cut film 2 may melt when the thin film solar cell 14 is used.

Moreover, the ultraviolet cut film 2 has a high softness | flexibility, its adhesiveness with an adjacent film is favorable, and what can cut water vapor | steam and oxygen is preferable.
The material which comprises the ultraviolet cut film 2 is arbitrary if the intensity | strength of an ultraviolet-ray can be weakened. Examples of the material include films formed by blending an ultraviolet absorber with an epoxy, acrylic, urethane, or ester resin. Further, a film in which a layer of an ultraviolet absorbent dispersed or dissolved in a resin (hereinafter referred to as “ultraviolet absorbing layer” as appropriate) is formed on a base film may be used.

  As the ultraviolet absorber, for example, salicylic acid-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ones can be used. Of these, benzophenone and benzotriazole are preferable. Examples of this include various aromatic organic compounds such as benzophenone and benzotriazole. In addition, a ultraviolet absorber may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

As described above, a film in which an ultraviolet absorbing layer is formed on a base film can be used as the ultraviolet absorbing film. Such a film can be produced, for example, by applying a coating solution containing an ultraviolet absorber on a substrate film and drying it.
Although the material of a base film is not specifically limited, For example, polyester is mentioned at the point from which the balance of heat resistance and a softness | flexibility is obtained.

  Application | coating can be performed by arbitrary methods. Examples thereof include reverse roll coating, gravure coating, kiss coating, roll brushing, spray coating, air knife coating, wire barber coating, pipe doctor method, impregnation / coating method and curtain coating method. In addition, these methods may be performed alone or in any combination of two or more.

  The solvent used for the coating solution is not particularly limited as long as it can uniformly dissolve or disperse the UV absorber. For example, a liquid resin can be used as a solvent, and examples thereof include various synthetic resins such as polyester, acrylic, polyamide, polyurethane, polyolefin, polycarbonate, or polystyrene. Further, for example, natural polymers such as gelatin and cellulose derivatives; water, alcohol mixed solutions such as water and ethanol, and the like can also be used as the solvent. Further, an organic solvent may be used as the solvent. If an organic solvent is used, it becomes possible to dissolve or disperse the pigment and the resin, and to improve the coatability. In addition, 1 type may be used for a solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

The coating solution may further contain a surfactant. Use of the surfactant improves the dispersibility of the ultraviolet absorbing dye in the resin. Thereby, in an ultraviolet absorption layer, generation | occurrence | production of the dent by the adhesion | attachment of the leakage of a micro bubble, a foreign material, etc. and / or a repellency in a drying process is suppressed.
As the surfactant, a known surfactant (cationic surfactant, anionic surfactant or nonionic surfactant) can be used. Among these, silicone surfactants or fluorine surfactants are preferable. In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.

In addition, the drying after apply | coating a coating liquid to a base film can employ | adopt well-known drying methods, such as hot air drying and drying by an infrared heater, for example. Among these, hot air drying with a high drying speed is preferable.
Examples of specific products of the ultraviolet cut film 2 include cut ace (MKV Plastic Co., Ltd.).

In addition, the ultraviolet cut film 2 may be formed with 1 type of material, and may be formed with 2 or more types of materials. Further, the ultraviolet cut film 2 may be formed of a single layer film, but may be a laminated film including two or more layers.
The thickness of the ultraviolet cut film 2 is not particularly defined, but is usually 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and usually 200 μm or less, preferably 180 μm or less, more preferably 150 μm or less. Increasing the thickness tends to increase the absorption of ultraviolet rays, and decreasing the thickness tends to increase the transmittance of visible light.

Although the ultraviolet cut film 2 should just be provided in the position which covers at least one part of the light-receiving surface 6a of the solar cell element 6, Preferably it is provided in the position which covers all the light-receiving surfaces 6a of the solar cell element 6. FIG.
However, the ultraviolet cut film 2 may be provided at a position other than the position covering the light receiving surface 6 a of the solar cell element 6.

[Gas barrier film 3]
The gas barrier film 3 is a film that prevents permeation of water and oxygen.

The solar cell element 6 tends to be vulnerable to moisture and oxygen. In particular, transparent electrodes such as ZnO: Al, compound semiconductor solar cell elements, and organic solar cell elements may be deteriorated by moisture and oxygen. Therefore, by covering the solar cell element 6 with the gas barrier film 3, the solar cell element 6 can be protected from water and oxygen, and the power generation capacity can be kept high.
The degree of moisture resistance required for the gas barrier film 3 varies depending on the type of the solar cell element 6 and the like. For example, when the solar cell element 6 is a compound semiconductor solar cell element, the water vapor permeability per unit area (1 m ² ) per day is 1 × 10 ⁻¹ g / m ² / day or less. Is preferably 1 × 10 ⁻² g / m ² / day or less, more preferably 1 × 10 ⁻³ g / m ² / day or less, and further preferably 1 × 10 ⁻⁴ g / m ^2. / Day or less is particularly preferable, 1 × 10 ⁻⁵ g / m ² / day or less is particularly preferable, and 1 × 10 ⁻⁶ g / m ² / day or less is particularly preferable.

Moreover, when the solar cell element 6 is an organic solar cell element, it is preferable that the water vapor permeability per unit area (1 m ² ) per day is 1 × 10 ⁻¹ g / m ² / day or less. It is more preferably 1 × 10 ⁻² g / m ² / day or less, further preferably 1 × 10 ⁻³ g / m ² / day or less, and further preferably 1 × 10 ⁻⁴ g / m ² / day. Among them, the following is particularly preferable, and it is particularly preferably 1 × 10 ⁻⁵ g / m ² / day or less, and particularly preferably 1 × 10 ⁻⁶ g / m ² / day or less. The more water vapor has to pass through, the lower the degradation caused by the reaction of the solar cell element 6 and the transparent electrode such as ZnO: Al of the element 6 with moisture, thus increasing the power generation efficiency and extending the life.

The degree of oxygen permeability required for the gas barrier film 3 varies depending on the type of the solar cell element 6 and the like. For example, when the solar cell element 6 is a compound semiconductor solar cell element, the oxygen permeability per unit area (1 m ² ) per day is 1 × 10 ⁻¹ cc / m ² / day / atm or less. Preferably, it is 1 × 10 ⁻² cc / m ² / day / atm or less, more preferably 1 × 10 ⁻³ cc / m ² / day / atm or less, and further preferably 1 × 10 2. ⁻⁴ cc / m ² / day / atm or less is particularly preferable, and 1 × 10 ⁻⁵ cc / m ² / day / atm or less is particularly preferable, and 1 × 10 ⁻⁶ cc / m ² / day. / Atm or less is particularly preferable. For example, when the solar cell element 6 is an organic solar cell element, the oxygen permeability per unit area (1 m ² ) per day is 1 × 10 ⁻¹ cc / m ² / day / atm or less. Preferably, it is 1 × 10 ⁻² cc / m ² / day / atm or less, more preferably 1 × 10 ⁻³ cc / m ² / day / atm or less, and further preferably 1 × 10 2. ⁻⁴ cc / m ² / day / atm or less is particularly preferable, and 1 × 10 ⁻⁵ cc / m ² / day / atm or less is particularly preferable, and 1 × 10 ⁻⁶ cc / m ² / day. / Atm or less is particularly preferable. The deterioration due to oxidation of the solar cell element 6 and the transparent electrode such as ZnO: Al of the element 6 is suppressed as the oxygen does not permeate.

  Conventionally, it has been difficult to mount the gas barrier film 3 having such a high moisture-proof and oxygen-blocking capability, so that a solar cell including an excellent solar cell element such as a compound semiconductor solar cell element and an organic solar cell element is realized. Although it was difficult to carry out, implementation of the thin film solar cell 14 which utilized the outstanding properties, such as a compound semiconductor type solar cell element and an organic solar cell element, becomes easy by applying such a gas barrier film 3.

  Further, the gas barrier film 3 is preferably one that transmits visible light from the viewpoint of not preventing the light absorption of the solar cell element 6. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. Preferably it is 90% or more, Especially preferably, it is 95% or more, Especially preferably, it is 97% or more. This is to convert more sunlight into electrical energy.

  Furthermore, since the thin film solar cell 14 is often heated by receiving light, it is preferable that the gas barrier film 3 also has heat resistance. From this viewpoint, the melting point of the constituent material of the gas barrier film 3 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably. It is 300 degrees C or less. By increasing the melting point, it is possible to reduce the possibility that the gas barrier film 3 is melted and deteriorated when the thin film solar cell 14 is used.

The specific configuration of the gas barrier film 3 is arbitrary as long as the solar cell element 6 can be protected from water. However, since the manufacturing cost increases as the amount of water vapor or oxygen that can permeate the gas barrier film 3 increases, it is preferable to use an appropriate film considering these points comprehensively.
Hereinafter, the configuration of the gas barrier film 3 will be described with examples.

The following two examples are preferable as the configuration of the gas barrier film 3.
The first example is a film in which an inorganic barrier layer is disposed on a plastic film substrate. In this case, the inorganic barrier layer may be formed only on one side of the plastic film substrate, or may be formed on both sides of the plastic film substrate. When forming on both surfaces, the number of inorganic barrier layers formed on both surfaces may be the same or different.

  The second example is a film in which a unit layer composed of two layers in which an inorganic barrier layer and a polymer layer are arranged adjacent to each other is formed on a plastic film substrate. At this time, a unit layer composed of two layers in which an inorganic barrier layer and a polymer layer are arranged adjacent to each other is regarded as one unit, and this unit layer is composed of one unit (one inorganic barrier layer and one polymer layer are combined into one unit). (Meaning of unit) may be formed, but two or more units may be formed. For example, 2 to 5 units may be laminated.

  The unit layer may be formed only on one side of the plastic film substrate, or may be formed on both sides of the plastic film substrate. When forming on both surfaces, the numbers of inorganic barrier layers and polymer layers formed on both surfaces may be the same or different. In addition, when forming a unit layer on a plastic film substrate, an inorganic barrier layer may be formed and then a polymer layer may be formed thereon, or after forming a polymer layer and forming an inorganic barrier layer. Also good.

(Plastic film substrate)
The plastic film substrate used for the gas barrier film 3 is not particularly limited as long as it is a film capable of holding the above-described inorganic barrier layer and polymer layer, and can be appropriately selected from the purpose of use of the gas barrier film 3 and the like.
Examples of the material for the plastic film substrate include polyester resin, polyarylate resin, polyethersulfone resin, fluorene ring-modified polycarbonate resin, alicyclic modified polycarbonate resin, and acryloyl compound. It is also preferable to use a condensation polymer containing spirobiindane or spirobichroman. Among the polyester resins, biaxially stretched polyethylene terephthalate (PET) or biaxially stretched polyethylene naphthalate (PEN) is excellent in thermal dimensional stability, and is preferably used as a plastic film substrate.

In addition, 1 type may be used for the material of a plastic film base material, and 2 or more types may be used together by arbitrary combinations and a ratio.
The thickness of the plastic film substrate is not particularly defined, but is usually 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and usually 200 μm or less, preferably 180 μm or less, more preferably 150 μm or less. Increasing the thickness tends to increase mechanical strength, and decreasing the thickness tends to increase flexibility.

  The plastic film substrate is preferably one that transmits visible light from the viewpoint of not preventing the solar cell element 6 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. Preferably it is 90% or more, Especially preferably, it is 95% or more, Especially preferably, it is 97% or more. This is to convert more sunlight into electrical energy.

  An anchor coat agent layer (anchor coat layer) may be formed on the plastic film substrate in order to improve adhesion to the inorganic barrier layer. Usually, the anchor coat layer is formed by applying an anchor coat agent. Examples of the anchor coating agent include polyester resins, urethane resins, acrylic resins, oxazoline group-containing resins, carbodiimide group-containing resins, epoxy group-containing resins, isocyanate-containing resins, and copolymers thereof. Among them, at least one resin selected from polyester resins, urethane resins and acrylic resins, and at least one resin selected from oxazoline group-containing resins, carbodiimide group-containing resins, epoxy group-containing resins and isocyanate group-containing resins. What combined the above resin is preferable. In addition, an anchor coat agent may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The thickness of the anchor coat layer is usually 0.005 μm or more, preferably 0.01 μm or more, and usually 5 μm or less, preferably 1 μm or less. If the thickness is less than or equal to the upper limit of this range, the slipperiness is good, and there is almost no peeling from the plastic film substrate due to the internal stress of the anchor coat layer itself. Moreover, if it is the thickness more than the lower limit of this range, a uniform thickness can be maintained and it is preferable.

  In addition, in order to improve the applicability and adhesion of the anchor coating agent to the plastic film substrate, the plastic film substrate may be subjected to a surface treatment such as normal chemical treatment or discharge treatment before application of the anchor coating agent. Good.

(Inorganic barrier layer)
The inorganic barrier layer is usually a layer formed of a metal oxide, nitride or oxynitride. In addition, the metal oxide, nitride, and oxynitride which form an inorganic barrier layer may be 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the metal oxide include oxides such as Si, Al, Mg, In, Ni, Sn, Zn, Ti, Cu, Ce, and Ta. Among these, in order to achieve both high barrier properties and high transparency, it is preferable to include aluminum oxide or silicon oxide, and it is particularly preferable to include silicon oxide from the viewpoint of moisture permeability and light transmittance.

The ratio of each metal atom to oxygen atom is also arbitrary, but in order to improve the transparency of the inorganic barrier layer and prevent coloring, the oxygen atom ratio should be extremely small from the stoichiometric ratio of the oxide. Is desirable. On the other hand, in order to improve the denseness of the inorganic barrier layer and increase the barrier property, it is desirable to reduce oxygen atoms. From this viewpoint, for example, when SiO _x is used as the metal oxide, the value of x is particularly preferably 1.5 to 1.8. For example, when AlO _x is used as the metal oxide, the value of x is particularly preferably 1.0 to 1.4.

  When the inorganic barrier layer is composed of two or more kinds of metal oxides, it is desirable that the metal oxide includes aluminum oxide and silicon oxide. Among them, when the inorganic barrier layer is made of aluminum oxide and silicon oxide, the ratio of aluminum and silicon in the inorganic barrier layer can be arbitrarily set, but the ratio of Si / Al is usually 1/9 or more, preferably 2/8 or more, and usually 9/1 or less, preferably 2/8 or less.

When the thickness of the inorganic barrier layer is increased, the barrier property tends to be increased. However, it is desirable to reduce the thickness in order to prevent cracking and prevent cracking when bent. Therefore, the appropriate thickness of the inorganic barrier layer is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably 200 nm or less.
Although there is no restriction | limiting in the film-forming method of an inorganic barrier layer, Generally, it can carry out by sputtering method, a vacuum evaporation method, an ion plating method, plasma CVD method etc. For example, the sputtering method can be formed by a reactive sputtering method using plasma using one or more metal targets and oxygen gas as raw materials.

(Polymer layer)
Any polymer can be used for the polymer layer, and for example, a film that can be formed in a vacuum chamber can be used. In addition, the polymer which comprises a polymer layer may use 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
A wide variety of compounds can be used as the compound that gives the polymer, and examples include the following (i) to (vii). In addition, 1 type may be used for a monomer and it may use 2 or more types together by arbitrary combinations and a ratio.

  (I) Examples include siloxanes such as hexamethyldisiloxane. An example of a method for forming a polymer layer in the case of using hexamethyldisiloxane is to introduce hexamethyldisiloxane as a vapor into a parallel plate type plasma apparatus using an RF electrode, to cause a polymerization reaction in the plasma, The polymer layer can be formed as a polysiloxane thin film by being deposited on a plastic film substrate.

  (Ii) Examples include paraxylylene such as diparaxylylene. As an example of a method for forming a polymer layer in the case of using diparaxylylene, first, the vapor of diparaxylylene is heated at 650 ° C. to 700 ° C. in a high vacuum to generate thermal radicals. Then, the radical monomer vapor is introduced into the chamber and adsorbed onto the plastic film substrate, and at the same time, the radical polymerization reaction proceeds to deposit polyparaxylylene to form a polymer layer.

  (Iii) For example, a monomer capable of alternately repeating addition polymerization of two kinds of monomers can be mentioned. The polymer thus obtained is a polyaddition polymer. Examples of the polyaddition polymer include polyurethane (diisocyanate / glycol), polyurea (diisocyanate / diamine), polythiourea (dithioisocyanate / diamine), polythioether urethane (bisethyleneurethane / dithiol), polyimine ( Bisepoxy / primary amine), polypeptide amide (bisazolactone / diamine) or polyamide (diolefin / diamide).

(Iv) Examples include acrylate monomers. The acrylate monomer includes monofunctional, bifunctional or polyfunctional acrylate monomers, and any of them may be used. However, in order to obtain an appropriate evaporation rate, degree of cure and / or cure rate, it is preferable to use a combination of two or more of the above acrylate monomers.
Examples of monofunctional acrylate monomers include aliphatic acrylate monomers, alicyclic acrylate monomers, ether acrylate monomers, cyclic ether acrylate monomers, aromatic acrylate monomers, hydroxyl group-containing acrylate monomers, or carboxy group-containing acrylate monomers. There are, but any can be used.

  (V) Monomers capable of obtaining a photocationically cured polymer, such as epoxy and oxetane, are exemplified. As an epoxy-type monomer, an alicyclic epoxy-type monomer, a bifunctional monomer, or a polyfunctional oligomer etc. are mentioned, for example. Examples of the oxetane-based monomer include monofunctional oxetane, bifunctional oxetane, and oxetane having a silsesquioxane structure.

(Vi) An example is vinyl acetate. When vinyl acetate is used as a monomer, polyvinyl alcohol is obtained by saponifying the polymer, and this polyvinyl alcohol can be used as a polymer.
(Vii) Examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride or itaconic anhydride. These constitute a copolymer with ethylene, and the copolymer can be used as a polymer. Furthermore, a mixture thereof, a mixture obtained by mixing glycidyl ether compounds, and a mixture with an epoxy compound can also be used as the polymer.

  There is no restriction | limiting in the polymerization method of a monomer when superposing | polymerizing the said monomer and producing | generating a polymer. However, the polymerization is usually carried out after a composition containing a monomer is applied or vapor deposited to form a film. As an example of the polymerization method, when a thermal polymerization initiator is used, the polymerization is started by contact heating with a heater or the like, or radiation heating such as infrared rays or microwaves. Moreover, when a photoinitiator is used, an active energy ray is irradiated and polymerization is started. Various light sources can be used when irradiating active energy rays, such as mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten-halogen radiation lamps, or irradiation light from sunlight. Can do. Further, electron beam irradiation or atmospheric pressure plasma treatment can also be performed.

Examples of the method for forming the polymer layer include a coating method and a vacuum film forming method.
When the polymer layer is formed by a coating method, for example, methods such as roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, and bar coating can be used. Moreover, you may make it apply | coat the coating liquid for polymer layer formation in mist form. In this case, the average particle diameter of the droplets may be adjusted to an appropriate range. For example, in the case of forming a coating liquid containing a polymerizable monomer in the form of a mist on a plastic film substrate, the droplets The average particle size of is usually 5 μm or less, preferably 1 μm or less.

On the other hand, when forming a polymer layer by a vacuum film-forming method, film-forming methods, such as vapor deposition and plasma CVD, are mentioned, for example.
The thickness of the polymer layer is not particularly limited, but is usually 10 nm or more, and is usually 5000 nm or less, preferably 2000 nm or less, more preferably 1000 nm or less. By increasing the thickness of the polymer layer, the uniformity of the thickness can be easily obtained, and structural defects of the inorganic barrier layer can be efficiently filled with the polymer layer, and the barrier property tends to be improved. In addition, by reducing the thickness of the polymer layer, the barrier property can be improved because the polymer layer itself is less likely to crack due to an external force such as bending.

Particularly suitable gas barrier film 3 includes, for example, a film obtained by vacuum-depositing SiO _x on a base film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN).
In addition, the gas barrier film 3 may be formed with 1 type of material, and may be formed with 2 or more types of materials. The gas barrier film 3 may be formed of a single layer film, but may be a laminated film including two or more layers.

  The thickness of the gas barrier film 3 is not particularly defined, but is usually 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and is usually 200 μm or less, preferably 180 μm or less, more preferably 150 μm or less. Increasing the thickness tends to increase gas barrier properties, and decreasing the thickness tends to increase flexibility and improve visible light transmittance.

  As long as the gas barrier film 3 covers the solar cell element 6 and can be protected from moisture and oxygen, the formation position is not limited. However, the front surface of the solar cell element 6 (surface on the light receiving surface side, lower surface in FIG. 2) and It is preferable to cover the back surface (the surface opposite to the light receiving surface; the upper surface in FIG. 2). This is because the front and back surfaces of the thin film solar cell 14 are often formed in a larger area than the other surfaces. In this embodiment, the gas barrier film 3 covers the front surface of the solar cell element 6, and a gas barrier film 9 described later covers the back surface of the solar cell element 6. In addition, when using a highly waterproof sheet such as a sheet in which a fluororesin film is bonded to both surfaces of an aluminum foil as the back sheet 10 described later, the getter material film 8 and / or the gas barrier film 9 may not be used depending on the application. Good.

[Getter material film 4]
The getter material film 4 is a film that absorbs moisture and / or oxygen. Some components of the solar cell element 6 are deteriorated by moisture as described above, and some are deteriorated by oxygen. Therefore, by covering the solar cell element 6 with the getter material film 4, the solar cell element 6 and the like are protected from moisture and / or oxygen, and the power generation capacity is kept high.

  Here, unlike the gas barrier film 3 as described above, the getter material film 4 does not prevent moisture permeation but absorbs moisture. By using a film that absorbs moisture, the getter material film 4 captures moisture that slightly enters the space formed by the gas barrier films 3 and 9 when the solar cell element 6 is covered with the gas barrier film 3 or the like. The influence of moisture on the solar cell element 6 can be eliminated.

The degree of water absorption capacity of the getter material film 4 is usually 0.1 mg / cm ² or more, preferably 0.5 mg / cm ² or more, more preferably 1 mg / cm ² or more. The higher this value, the higher the water absorption capacity, and the deterioration of the solar cell element 6 can be suppressed. Moreover, although there is no restriction | limiting in an upper limit, it is usually 10 mg / cm < ² > or less.
Further, when the solar cell element 6 is covered with the gas barrier films 3 and 9 or the like by the getter material film 4 absorbing oxygen, the oxygen that slightly enters the space formed by the gas barrier films 3 and 9 is obtained as the getter material. The film 4 can capture and eliminate the influence of oxygen on the solar cell element 6.

  Furthermore, the getter material film 4 is preferably one that transmits visible light from the viewpoint of not preventing the solar cell element 6 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. Preferably it is 90% or more, Especially preferably, it is 95% or more, Especially preferably, it is 97% or more. This is to convert more sunlight into electrical energy.

  Furthermore, since the thin film solar cell 14 is often heated by receiving light, the getter material film 4 preferably has heat resistance. From this viewpoint, the melting point of the constituent material of the getter material film 4 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably. Is 300 ° C. or lower. By increasing the melting point, it is possible to reduce the possibility that the getter material film 4 melts and deteriorates when the thin-film solar cell 14 is used.

  The material constituting the getter material film 4 is arbitrary as long as it can absorb moisture and / or oxygen. Examples of the material include alkali metal, alkaline earth metal or alkaline earth metal oxides; alkali metal or alkaline earth metal hydroxides; silica gel, zeolitic compounds, magnesium sulfate. And sulfates such as sodium sulfate and nickel sulfate; and organometallic compounds such as aluminum metal complexes and aluminum oxide octylates. Specifically, examples of the alkaline earth metal include Ca, Sr, and Ba. Examples of the alkaline earth metal oxide include CaO, SrO, and BaO. In addition, Zr-Al-BaO and aluminum metal complexes are also included. Specific product names include, for example, OleDry (Futaba Electronics).

Examples of the substance that absorbs oxygen include activated carbon, silica gel, activated alumina, molecular sieve, magnesium oxide, and iron oxide. In addition, Fe, Mn, Zn, and inorganic salts such as sulfates, chlorides, and nitrates of these metals are also included.
In addition, the getter material film 4 may be formed of one type of material or may be formed of two or more types of materials. The getter material film 4 may be formed of a single layer film, but may be a laminated film including two or more layers.

The thickness of the getter material film 4 is not particularly specified, but is usually 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and usually 200 μm or less, preferably 180 μm or less, more preferably 150 μm or less. Increasing the thickness tends to increase mechanical strength, and decreasing the thickness tends to increase flexibility.
The formation position of the getter material film 4 is not limited as long as it is in the space formed by the gas barrier films 3 and 9, but the front surface of the solar cell element 6 (the surface on the light receiving surface side, the lower surface in FIG. 2). And it is preferable to cover the back surface (surface opposite to the light receiving surface; upper surface in FIG. 2). This is because, in the thin film solar cell 14, the front and back surfaces are often formed in a larger area than the other surfaces, and therefore moisture and oxygen tend to enter through these surfaces. From this viewpoint, the getter material film 4 is preferably provided between the gas barrier film 3 and the solar cell element 6. In this embodiment, the getter material film 4 covers the front surface of the solar cell element 6, a getter material film 8 described later covers the back surface of the solar cell element 6, and the getter material films 4 and 8 are respectively the solar cell element 6 and the gas barrier film 3. , 9 are located between them. In addition, when using a highly waterproof sheet such as a sheet obtained by bonding a fluororesin film on both surfaces of an aluminum foil as the back sheet 10 described later, the getter material film 8 and / or the gas barrier film 9 may not be used depending on the application. .

  The getter material film 4 can be formed by any method depending on the type of the water-absorbing agent or desiccant. For example, a method in which a film in which the water-absorbing agent or desiccant is dispersed is attached with a pressure-sensitive adhesive, The method of apply | coating this solution with a spin coat method, the inkjet method, or a dispenser method etc. can be used. Further, a film forming method such as a vacuum evaporation method or a sputtering method may be used.

  As a film for a water absorbing agent or a desiccant, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, or the like can be used. Among these, a film of polyethylene resin, fluorine resin, cyclic polyolefin resin or polycarbonate resin is preferable. In addition, the said resin may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

[Sealing material 5]
The sealing material 5 is a film that reinforces the solar cell element 6. Since the solar cell element 6 is thin, the strength is usually weak, and thus the strength of the thin film solar cell tends to be weak. However, the strength can be maintained high by the sealing material 5.
Moreover, it is preferable that the sealing material 5 has high strength from the viewpoint of maintaining strength of the thin-film solar cell 14.

The specific strength is related to the strength of the weatherproof protective film 1 other than the sealing material 5 and the strength of the back sheet 10 and is generally difficult to define, but the thin film solar cell 14 as a whole has good bending workability. However, it is desirable to have a strength that does not cause peeling of the bent portion.
In addition, the sealing material 5 is preferably one that transmits visible light from the viewpoint of not preventing the solar cell element 6 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. Preferably it is 90% or more, Especially preferably, it is 95% or more, Especially preferably, it is 97% or more. This is to convert more sunlight into electrical energy.

  Furthermore, since the thin film solar cell 14 is often heated by receiving light, it is preferable that the sealing material 5 also has heat resistance. From this viewpoint, the melting point of the constituent material of the sealing material 5 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably. Is 300 ° C. or lower. By increasing the melting point, it is possible to reduce the possibility that the sealing material 5 melts and deteriorates when the thin film solar cell 14 is used.

  The thickness of the sealing material 5 is not particularly defined, but is usually 100 μm or more, preferably 150 μm or more, more preferably 200 μm or more, and usually 700 μm or less, preferably 600 μm or less, more preferably 500 μm or less. Increasing the thickness tends to increase the strength of the thin-film solar cell 14 as a whole, and decreasing the thickness tends to increase flexibility and improve visible light transmittance.

  As a material which comprises the sealing material 5, what used the ethylene-vinyl acetate copolymer (EVA) resin composition for the film (EVA film) etc. can be used, for example. In order to improve weather resistance, the EVA film is usually blended with a crosslinking agent to form a crosslinked structure. As the crosslinking agent, an organic peroxide that generates radicals at 100 ° C. or higher is generally used. Examples of such organic peroxides include 2,5-dimethylhexane, 2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 3- Di-t-butyl peroxide or the like can be used. The compounding amount of these organic peroxides is usually 5 parts by weight or less, preferably 3 parts by weight or less, and usually 1 part by weight or more with respect to 100 parts by weight of the EVA resin. In addition, 1 type may be used for a crosslinking agent and it may use 2 or more types together by arbitrary combinations and a ratio.

  This EVA resin composition may contain a silane coupling agent for the purpose of improving the adhesive strength. Examples of the silane coupling agent used for this purpose include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris- (β-methoxyethoxy) silane, γ-methacryloxypropyltri Examples thereof include methoxysilane and β- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane. The compounding amount of these silane coupling agents is usually 5 parts by weight or less, preferably 2 parts by weight or less, and usually 0.1 parts by weight or more with respect to 100 parts by weight of the EVA resin. In addition, 1 type may be used for a silane coupling agent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Furthermore, in order to improve the gel fraction of the EVA resin and improve the durability, a crosslinking aid may be included in the EVA resin composition. Examples of the crosslinking aid provided for this purpose include monofunctional crosslinking aids such as trifunctional crosslinking aids such as triallyl isocyanurate or triallyl isocyanate. The amount of these crosslinking aids is usually 10 parts by weight or less, preferably 5 parts by weight or less, and usually 1 part by weight or more with respect to 100 parts by weight of the EVA resin. In addition, 1 type may be used for a crosslinking adjuvant, and 2 or more types may be used together by arbitrary combinations and a ratio.

Furthermore, for the purpose of improving the stability of the EVA resin, the EVA resin composition may contain, for example, hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, or methylhydroquinone. These compounding quantities are normally 5 weight part or less with respect to 100 weight part of EVA resin.
However, since the EVA resin cross-linking process requires a relatively long time of about 1 to 2 hours, it may cause a reduction in the production rate and production efficiency of the thin-film solar cell 14. In addition, when used for a long time, the decomposition gas (acetic acid gas) of the EVA resin composition or the vinyl acetate group of the EVA resin itself may adversely affect the solar cell element 6 and reduce the power generation efficiency.
Therefore, as the sealing material 5, in addition to the EVA film, a copolymer film made of a propylene / ethylene / α-olefin copolymer can also be used. As this copolymer, the thermoplastic resin composition with which the following component 1 and the component 2 were mix | blended is mentioned, for example.

Component 1: The propylene polymer is usually 0 part by weight or more, preferably 10 parts by weight or more, and usually 70 parts by weight or less, preferably 50 parts by weight or less.
Component 2: The soft propylene copolymer is 30 parts by weight or more, preferably 50 parts by weight or more, and is usually 100 parts by weight or less, preferably 90 parts by weight or less.
The total amount of component 1 and component 2 is 100 parts by weight. As described above, when component 1 and component 2 are in the preferred ranges, the moldability of the encapsulant 5 into a sheet is good, and the resulting encapsulant 5 has good heat resistance, transparency, and flexibility. Therefore, it is suitable for the thin film solar cell 14.

The thermoplastic resin composition in which the above components 1 and 2 are blended has a melt flow rate (ASTM D 1238, 230 degrees, load 2.16 kg), usually 0.0001 g / 10 min or more. It is 1000 g / 10 min or less, preferably 900 g / 10 min or less, more preferably 800 g / 10 min or less.
The melting point of the thermoplastic resin composition containing component 1 and component 2 is usually 100 ° C. or higher, preferably 110 ° C. or higher. Moreover, it is 140 degrees C or less normally, Preferably it is 135 degrees C or less.

Density of The thermoplastic resin composition components 1 and 2 is blended is preferably from 0.98 g / cm ³ or less, more preferably 0.95 g / cm ³ or less, more preferably 0.94 g / cm ³ or less .
In this sealing material 5, it is possible to mix | blend a coupling agent with the said component 1 and component 2 as an adhesion promoter with respect to a plastics. As the coupling agent, silane, titanate, and chromium coupling agents are preferably used, and a silane coupling agent (silane coupling agent) is particularly preferably used.

  Known silane coupling agents can be used and are not particularly limited. For example, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxy-ethoxysilane), γ-glycidoxypropyl-tri Examples include piltrimethoxysilane or γ-aminopropyltriethoxysilane. In addition, 1 type may be used for a coupling agent and it may use 2 or more types together by arbitrary combinations and a ratio.

In addition, these usually contain 0.1 parts by weight or more of the silane coupling agent, and usually 5 parts by weight or less, preferably 100 parts by weight of the thermoplastic resin composition (total amount of Component 1 and Component 2). It is desirable to contain 3 parts by weight or less.
The coupling agent may be grafted to the thermoplastic resin composition using an organic peroxide. In this case, it is desirable to contain 0.1 to 5 parts by weight of the coupling agent with respect to 100 parts by weight of the thermoplastic resin composition (total amount of component 1 and component 2). Even when a silane-grafted thermoplastic resin composition is used, the same or better adhesiveness as that of the silane coupling agent blend can be obtained with respect to glass or plastic.

When the organic peroxide is used, the organic peroxide is usually 0.001 part by weight or more, preferably 0.01 part by weight with respect to 100 parts by weight of the thermoplastic resin composition (total amount of Component 1 and Component 2). The amount is usually 5 parts by weight or less, preferably 3 parts by weight or less.
Further, a copolymer made of an ethylene / α-olefin copolymer can be used as the sealing material 5. As this copolymer, a laminate film having a hot tack property of 5 to 25 ° C., which is formed by laminating a resin composition for a sealing material comprising the following components A and B and a substrate, is exemplified.

Component A: ethylene resin.
Component B: a copolymer of ethylene and an α-olefin having the following properties (a) to (d).
(A) Density is 0.86-0.935 g / cm ³ .
(B) Melt flow rate (MFR) is 1 to 50 g / 10 min.
(C) There is one peak in the elution curve obtained by temperature rising elution fractionation (TREF), and the peak temperature is 100 ° C. or lower.
(D) The integrated elution amount by temperature rising elution fractionation (TREF) is 90% or more at 90 ° C.
The blending ratio (component A / component B) of component A and component B is usually 50/50 or more, preferably 55/45 or more, more preferably 60/40 or more, and usually 99 / 1 or less, preferably 90/10 or less, more preferably 85/15 or less. Increasing the amount of component B tends to increase transparency and heat sealability, and decreasing the amount of component B tends to increase the workability of the film.

  The melt flow rate (MFR) of the resin composition for a sealing material produced by blending component A and component B is usually 2 g / 10 minutes or more, preferably 3 g / 10 minutes or more, and usually 50 g / 10 minutes. Hereinafter, it is preferably 40 g / 10 min or less. In addition, the measurement and evaluation of MFR can be implemented by the method based on JISK7210 (190 degreeC, 2.16kg load).

The melting point of the encapsulant resin composition is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and is usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. By increasing the melting point, the possibility of melting and deterioration during use of the thin-film solar cell 14 can be reduced.
The density of the resin composition for a sealing material is preferably 0.80 g / cm ³ or more, more preferably 0.85 g / cm ³ or more, and preferably 0.98 g / cm ³ or less, 0.95 g / cm ^3. The following is more preferable, and 0.94 g / cm ³ or less is more preferable. The measurement and evaluation of density can be performed by a method based on JIS K7112.

Further, in the encapsulant 5 using the ethylene / α-olefin copolymer, a coupling agent can be used as in the case of using the propylene / ethylene / α-olefin copolymer.
Since the sealing material 5 described above does not generate a decomposition gas derived from the material, there is no adverse effect on the solar cell element 6, and good heat resistance, mechanical strength, flexibility (solar cell sealing property) and transparency. Have sex. In addition, since a material cross-linking step is not required, the manufacturing time of the thin film solar cell 14 during sheet molding can be greatly shortened, and the thin film solar cell 14 after use can be easily recycled.

In addition, the sealing material 5 may be formed with 1 type of material, and may be formed with 2 or more types of materials. Moreover, although the sealing material 5 may be formed with the single layer film, the laminated | multilayer film provided with the film of 2 or more layers may be sufficient as it.
The thickness of the sealing material 5 is usually 2 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and usually 500 μm or less, preferably 300 μm or less, more preferably 100 μm or less. Increasing the thickness tends to increase mechanical strength, and decreasing the thickness tends to increase flexibility and light transmittance.

  Although there is no restriction | limiting in the position which provides the sealing material 5, Usually, it provides so that the solar cell element 6 may be inserted | pinched. This is for reliably protecting the solar cell element 6. In this embodiment, the sealing material 5 and the sealing material 7 are provided on the front surface and the back surface of the solar cell element 6, respectively.

[Solar cell element 6]
The solar cell element 6 is the same as the above-described photoelectric conversion element.

-Connection between solar cell elements Only one solar cell element 6 may be provided for each thin film solar cell 14, but usually two or more solar cell elements 6 are provided. The specific number of solar cell elements 6 may be set arbitrarily. When a plurality of solar cell elements 6 are provided, the solar cell elements 6 are often arranged in an array.

When a plurality of solar cell elements 6 are provided, the solar cell elements 6 are usually electrically connected to each other, and electricity generated from the connected group of solar cell elements 6 is taken out from a terminal (not shown). At this time, the solar cell elements are usually connected in series in order to increase the voltage.
Thus, when connecting the solar cell elements 6, it is preferable that the distance between the solar cell elements 6 is small, and the clearance between the solar cell element 6 and the solar cell element 6 is preferably narrow. This is because the light receiving area of the solar cell element 6 is widened to increase the amount of received light, and the amount of power generated by the thin film solar cell 14 is increased.

[Encapsulant 7]
The sealing material 7 is a film similar to the sealing material 5 described above, and the same material as the sealing material 7 can be used in the same manner except that the arrangement position is different.
Moreover, since the constituent member on the back side of the solar cell element 6 does not necessarily need to transmit visible light, a member that does not transmit visible light can be used.

[Getter material film 8]
The getter material film 8 is the same film as the getter material film 4 described above, and the same material as the getter material film 4 can be used as necessary, except for the arrangement position.
Moreover, since the constituent member on the back side of the solar cell element 6 does not necessarily need to transmit visible light, a member that does not transmit visible light can be used. It is also possible to use a film containing more water or oxygen absorbent than the getter material film 4. As such an absorbent, CaO, BaO, Zr-Al-BaO, etc. are mentioned as a moisture absorbent, and activated carbon, molecular sieve, etc. are mentioned as an oxygen absorbent.

[Gas barrier film 9]
The gas barrier film 9 is the same film as the gas barrier film 3 described above, and the same material as the gas barrier film 9 can be used as necessary except that the arrangement position is different.
Moreover, since the constituent member on the back side of the solar cell element 6 does not necessarily need to transmit visible light, a member that does not transmit visible light can be used.

[Backsheet 10]
The back sheet 10 is the same film as the weather-resistant protective film 1 described above, and the same material as the weather-resistant protective film 1 can be used in the same manner except that the arrangement position is different. In addition, if the back sheet 10 is difficult to permeate water and oxygen, the back sheet 10 can also function as a gas barrier layer.

Moreover, since the constituent member on the back side of the solar cell element 6 does not necessarily need to transmit visible light, a member that does not transmit visible light can be used. For this reason, it is particularly preferable to use the following (i) to (iv) as the backsheet 10.
(I) As the back sheet 10, it is possible to use various resin films or sheets having excellent strength and weather resistance, heat resistance, water resistance and / or light resistance. For example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine Resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate or polyethylene naphthalate, various polyamide resins such as nylon, polyimide resin, polyamideimide resin, polyaryl phthalate resin , Silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin or other resin It can be used. Among these resin sheets, it is preferable to use a fluorine resin, a cyclic polyolefin resin, a polycarbonate resin, a poly (meth) acrylic resin, a polyamide resin, or a polyester resin sheet. In addition, these may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

(Ii) As the back sheet 10, a metal thin film can also be used. For example, corrosion-resistant aluminum metal foil, stainless steel thin film, and the like can be mentioned. In addition, the said metal may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
(Iii) As the back sheet 10, for example, a highly waterproof sheet in which a fluorine resin film is bonded to both surfaces of an aluminum foil may be used. Examples of the fluorine resin include ethylene monofluoride (trade name: Tedlar, manufactured by DuPont), polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and ethylene or propylene (ETFE), and a vinylidene fluoride resin. (PVDF) or vinyl fluoride resin (PVF). In addition, 1 type may be used for fluororesin and it may use 2 or more types together by arbitrary combinations and a ratio.

  (Iv) As the back sheet 10, for example, an inorganic oxide vapor-deposited film is provided on one side or both sides of the base film, and furthermore, the base film provided with the inorganic oxide vapor-deposited film has heat resistance on both sides. What laminated | stacked the property polypropylene-type resin film may be used. Usually, when a polypropylene resin film is laminated on the base film, the lamination is performed by laminating with a laminating adhesive. By providing an inorganic oxide vapor-deposited film, it can be used as a back sheet 10 having excellent moisture resistance that prevents intrusion of moisture and / or oxygen.

・ Base film Basically, the base film is excellent in close adhesion with inorganic oxide deposition film, etc., excellent in strength, weather resistance, heat resistance, water resistance, and light resistance. Resin films can be used. For example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine Resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate or polyethylene naphthalate, various polyamide resins such as nylon, polyimide resin, polyamideimide resin, polyaryl phthalate resin , Silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfone resins, polyurethane resins, acetal resins, cellulose resins, and other resins. It is possible to use the beam. Among these, it is preferable to use a film of a fluorine resin, a cyclic polyolefin resin, a polycarbonate resin, a poly (meth) acrylic resin, a polyamide resin, or a polyester resin.

  Among the various resin films as described above, for example, a fluororesin film such as polytetrafluoroethylene (PTFE), vinylidene fluoride resin (PVDF), or vinyl fluoride resin (PVF) is used. It is more preferable. Further, among these fluororesin films, in particular, a fluororesin film made of polyvinyl fluoride resin (PVF) or a copolymer of tetrafluoroethylene and ethylene or propylene (ETFE) is particularly preferable from the viewpoint of strength and the like. preferable. In addition, the said resin may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

Of the various resin films as described above, it is more preferable to use a film of a cyclic polyolefin resin such as cyclopentadiene and a derivative thereof or cyclohexadiene and a derivative thereof.
The film thickness of the base film is usually 12 μm or more, preferably 20 μm or more, and is usually 300 μm or less, preferably 200 μm or less.

-Vapor deposition film of an inorganic oxide As a vapor deposition film of an inorganic oxide, basically any thin film on which a metal oxide is deposited can be used. For example, a deposited film of an oxide of silicon (Si) or aluminum (Al) can be used. At this time, for example, SiO _x (x = 1.0 to 2.0) can be used as silicon oxide, and for example, AlO _x (x = 0.5 to 1.5) can be used as aluminum oxide. .

In addition, the kind of metal and inorganic oxide to be used may be 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
The film thickness of the inorganic oxide vapor deposition film is usually 50 mm or more, preferably 100 mm or more, and is usually 4000 mm or less, preferably 1000 mm or less.
As a method for forming the deposited film, a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method can be used. As a specific example, on one surface of the base film, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is supplied. An oxygen oxide vapor or the like can be used as a gas, and a vapor deposition film of an inorganic oxide such as silicon oxide can be formed using a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like.

-Polypropylene-type resin film As a polypropylene-type resin, the homopolymer of propylene or the copolymer of propylene and another monomer (for example, alpha-olefin etc.) can be used, for example. Moreover, an isotactic polymer can also be used as a polypropylene resin.
The melting point of the polypropylene resin is usually 164 ° C or higher, and is usually 170 ° C or lower. The specific gravity of the polypropylene resin is usually 0.90 or more, and usually 0.91 or less. The molecular weight of the polypropylene resin is usually 100,000 or more, and usually 200,000 or less.

  Polypropylene resins are largely controlled by their crystallinity, but high isotactic polymers have excellent tensile strength and impact strength, good heat resistance and bending fatigue strength, and workability. Is very good.

-Adhesive When laminating a polypropylene resin film on a base film, an adhesive for laminating is usually used. Thereby, a base film and a polypropylene resin film are laminated | stacked via the adhesive bond layer for lamination.

  Examples of the adhesive constituting the adhesive layer for laminating include, for example, a polyvinyl acetate adhesive, a polyacrylate adhesive, a cyanoacrylate adhesive, an ethylene copolymer adhesive, a cellulose adhesive, and a polyester adhesive. Adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives, phenol resin adhesives, epoxy adhesives, polyurethane adhesives, reactive (meth) acrylic adhesives, silicone adhesives, etc. Is mentioned. In addition, 1 type may be used for an adhesive agent and it may use 2 or more types together by arbitrary combinations and a ratio.

The composition system of the adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, or a dispersion type. Further, the property may be any of film / sheet, powder, solid and the like. Furthermore, the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a hot melt type, or a hot pressure type.
The adhesive can be applied by, for example, a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, or a printing method. The coating amount is usually preferably 0.1 g / m ² or more in a dry state, and usually 10 g / m ² or less.

[Dimensions]
The thin film solar cell 14 of the present embodiment is usually a thin film member. Thus, by forming the thin film solar cell 14 as a film-like member, the thin film solar cell 14 can be easily installed in a building material, an automobile, an interior, or the like. The thin-film solar cell 14 is light and difficult to break, and thus a highly safe solar cell can be obtained and can be applied to a curved surface, so that it can be used for more applications. Since it is thin and light, it is preferable in terms of distribution such as transportation and storage. Furthermore, since it is in the form of a film, it can be manufactured in a roll-to-roll manner, and the cost can be greatly reduced.

  Although there is no restriction | limiting in the specific dimension of the thin film solar cell 14, The thickness is 300 micrometers or more normally, Preferably it is 500 micrometers or more, More preferably, it is 700 micrometers or more, Moreover, it is 3000 micrometers or less normally, Preferably it is 2000 micrometers or less, More preferably. It is 1500 micrometers or less.

[Production method]
Although there is no restriction | limiting in the manufacturing method of the thin film solar cell 14 of this embodiment, For example, between the weather-resistant protective film 1 and the back sheet | seat 10, the 1 or 2 or more solar cell element 6 was connected in series or in parallel. The product can be manufactured by laminating with a general vacuum laminating apparatus together with the ultraviolet cut film 2, the gas barrier films 3, 9, the getter material films 4, 8, and the sealing materials 5, 7. At this time, the heating temperature is usually 130 ° C. or higher, preferably 140 ° C. or higher, and is usually 180 ° C. or lower, preferably 170 ° C. or lower. The heating time is usually 10 minutes or longer, preferably 20 minutes or longer, usually 100 minutes or shorter, preferably 90 minutes or shorter. The pressure is usually 0.001 MPa or more, preferably 0.01 MPa or more, and usually 0.2 MPa or less, preferably 0.1 MPa or less. By setting the pressure within this range, sealing can be reliably performed, and the sealing materials 5 and 7 from the end can be prevented from protruding or reduced in film thickness due to over-pressurization, thereby ensuring dimensional stability.

[Usage]
There is no restriction | limiting in the use of the thin film solar cell 14 mentioned above, It is arbitrary. For example, as schematically shown in FIG. 3, a solar cell module 13 in which a thin film solar cell 14 is provided on a certain base material 12 is prepared and used at a place of use. As a specific example, when a building material plate is used as the base material 12, a thin film solar cell 14 is provided on the surface of the plate material to produce a solar cell panel as the solar cell module 13, and this solar cell panel is attached to the outer wall of the building. It can be installed and used.

  The substrate 12 is a support member that supports the solar cell element 6. Examples of the material for forming the substrate 12 include inorganic materials such as glass, sapphire, and titania; polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, fluorine. Organic materials such as resin film, vinyl chloride, polyethylene, cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene; paper materials such as paper or synthetic paper; metals such as stainless steel, titanium or aluminum For example, a composite material such as a material whose surface is coated or laminated in order to impart insulating properties can be used. In addition, 1 type may be used for the material of a base material, and 2 or more types may be used together by arbitrary combinations and a ratio. Moreover, carbon fiber may be included in these organic materials or paper materials to reinforce the mechanical strength.

  Examples of fields to which the thin film solar cell of the present invention is applied include solar cells for building materials, solar cells for automobiles, solar cells for interiors, solar cells for railways, solar cells for ships, solar cells for airplanes, solar cells for spacecraft. It is suitable for use in batteries, solar cells for home appliances, solar cells for mobile phones, solar cells for toys, and the like. Specific examples include the following.

1. Architectural use
1.1 Solar cell as a house roof material When a roof plate or the like is used as a base material, a thin film solar cell is provided on the surface of the plate material to produce a solar cell panel as a solar cell unit. Just install on the roof. Moreover, a roof tile can also be used directly as a base material. The solar cell of the present invention is suitable because it can be brought into close contact with the roof tiles by taking advantage of its flexibility.

1.2 Rooftop Can be installed on the rooftop of a building. A solar cell unit in which a thin film solar cell is provided on a base material can be prepared and installed on the roof of a building. At this time, it is desirable to use a waterproof sheet together with the base material to have a waterproof action. Furthermore, taking advantage of the property that the thin film solar cell of the present invention has flexibility, it can be brought into close contact with a roof that is not flat, for example, a folded roof. In this case, it is desirable to use a waterproof sheet in combination.

1.3 Toplight The thin-film solar cell of the present invention can also be used as an exterior at the entrance or at the atrium. Curves are often used for entrances and the like that have undergone some design processing, and in such a case, the flexibility of the thin film solar cell of the present invention is utilized. In addition, there is a case of see-through in an entrance or the like. In such a case, the green color of the organic solar cell is suitable because a design aesthetic can be obtained in an era when environmental measures are regarded as important.

1.4 Wall When a building material plate is used as the base material, a thin film solar cell is provided on the surface of the plate material to produce a solar cell panel as a solar cell unit, and this solar cell panel is installed on the outer wall of the building. Use it. It can also be installed on curtain walls. In addition, it can be attached to a spandrel or a vertical.

  In this case, the shape of the substrate is not limited, but a plate material is usually used. Moreover, what is necessary is just to set the material of a base material, a dimension, etc. arbitrarily according to the use environment. As an example of such a substrate, Alpolic (registered trademark; manufactured by Mitsubishi Plastics) and the like can be mentioned.

1.5 windows It can also be used for see-through windows. The green color of the organic solar cell is preferable because a design aesthetic can be obtained in an era when environmental measures are important.

1.6 Others Can be used for eaves, louvers, handrails, etc. as other architectural exteriors. Even in such a case, the flexibility of the thin film solar cell of the present invention is suitable for these applications.

2. Interior The thin film solar cell of this invention can also be attached to the slat of a blind. Since the thin-film solar cell of the present invention is lightweight and rich in flexibility, such a use is possible. Further, the contents window can be used by utilizing the characteristic that the organic solar cell element is see-through.

3. Vegetable factories Although the number of plant factories that utilize illumination light such as fluorescent lamps is increasing, the current situation is that it is difficult to reduce the cultivation cost due to the electricity bill for lighting and the replacement cost of the light source. Then, the thin film solar cell of this invention can be installed in a vegetable factory, and the illumination system combined with LED or the fluorescent lamp can be produced.

At this time, it is preferable to use an illumination system that combines an LED having a longer life than a fluorescent lamp and the solar cell of the present invention, because the cost required for illumination can be reduced by about 30% compared to the current situation.
Moreover, the solar cell of this invention can also be used for the roof and side wall of the reefer container (reefer container) which conveys vegetables etc. at fixed temperature.

4). Road Material / Civil Engineering The thin film solar cell of the present invention can be used for an outer wall of a parking lot, a sound insulation wall of an expressway, an outer wall of a water purification plant, and the like.

5. Automobile The thin film solar cell of the present invention can be used on the surface of an automobile bonnet, roof, trunk lid, door, front fender, rear fender, pillar, bumper or rearview mirror. The roof includes the roof of the truck bed. The obtained electric power can be supplied to any of a traveling motor, a motor driving battery, an electrical component, and an electrical component battery. By providing the power generation status in the solar cell panel and the control means for selecting according to the power usage status in the motor for driving, the battery for driving the motor, the electrical equipment, and the battery for electrical equipment, the obtained power is It can be used properly and efficiently.
In the above case, the shape of the substrate 12 is not limited, but a plate material is usually used. Moreover, what is necessary is just to set the material of the base material 12, a dimension, etc. arbitrarily according to the use environment.

  Examples of such a substrate 12 include Alpolic (registered trademark; manufactured by Mitsubishi Plastics) and the like.

  Examples The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The items described in the examples were measured by the following methods.

[Method for measuring weight average molecular weight and number average molecular weight]
The weight average molecular weight and number average molecular weight in terms of polystyrene were determined by gel permeation chromatography (GPC). As the columns, Shim-pack GPC-803 and GPC-804 (manufactured by Shimadzu Corporation, inner diameter 8.0 mm, length 30 cm) were connected in series one by one. LC-10AT as a pump, CTO-10A as an oven, a differential refractive index detector (manufactured by Shimadzu Corporation: RID-10A) as a detector, and a UV-vis detector (manufactured by Shimadzu Corporation: SPD-10A) as a detector. Using. The polymer was dissolved in tetrahydrofuran (THF), and 5 μL of the resulting solution was injected into the column. Measurement was performed at a flow rate of 1.0 mL / min using THF as the mobile phase. The analysis was performed using LC-Solution (manufactured by Shimadzu Corporation).

[Elemental analysis]
About Pd and Sn, after wet-decomposing the sample, Pd and Sn in the decomposition solution were quantified by a calibration curve method using an ICP mass spectrometer (ICP mass spectrometer 7500ce type manufactured by Agilent Technologies). For Br ⁻ and I ⁻ , the sample is combusted with a sample combustion device (sample combustion device QF-02 type manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the combustion gas is absorbed in an alkaline absorbing liquid containing a reducing agent. The Br ⁻ and I ⁻ therein were quantified by a calibration curve method using an ICP mass spectrometer (ICP mass spectrometer 7500ce type manufactured by Agilent Technologies).

[Absorption spectrum]
Hitachi spectrophotometer U-3500 was used for the absorption spectrum measurement. A chloroform solution of the copolymer (adjusted so that the absorbance maximum was 0.8 or less) was measured using a 1 cm square quartz cell. The spectra of the copolymer A1, the copolymer A2, the copolymer A3, and the copolymer B were normalized with the absorbance at an absorption wavelength of 610 nm being 0.25. The spectra of copolymer A2 and copolymer C were normalized by setting the absorbance maximum of the obtained spectrum to 0.38.

[Measurement of X-ray diffraction (XRD) spectrum]
The X-ray diffraction (XRD) spectrum was measured using an X-ray diffractometer (XRD, RINT-2000 manufactured by Rigaku) and using Cu as the counter cathode.

[Minimum unoccupied molecular orbital (LUMO) measurement of electron extraction layer material]
The LUMO of various electron extraction layer materials was calculated by cyclic voltammogram measurement. The measurement was performed at room temperature, and a glassy carbon electrode was used for the working electrode, a platinum electrode for the counter electrode, and Ag / Ag ⁺ for the reference electrode. An acetonitrile (ACN) solution containing tetrabutylammonium perchlorate (TBAP) (0.1 M) was used as an electrolyte. The concentration of the electron extraction layer material was about 0.5 mM. The potential was based on the oxidation-reduction potential of ferrocene. From the obtained first reduction potential value (E _1/2 ^red1 ), LUMO is calculated using the following equation (see Non-Patent Document: Nat. Mater. 2007, 6, 521), and the obtained first Based on the value of one reduction potential, the LUMO value of PCBM (PCBM manufactured by Frontier Carbon Co., Ltd .: 1- (3-methoxycarbonyl) propyl-1-phenyl (6,6) -C60) is set to −3.80 eV (non-patented). The value of LUMO was calculated from the relative value in the case of J. Am. Chem. Soc. 2008, 130, 15429-15436).
LUMO level = − (E _1/2 ^red1 +4.8)

[Measurement of glass transition temperature (Tg) by DSC method]
About 4 mg of sample is put in an aluminum sample container and measured using a differential thermal scanning calorimeter manufactured by SII Nanotechnology Co., Ltd. under the conditions of N ₂ gas 50 ml / min and heating rate 10 ° C./min. Was determined by

[Evaluation of photoelectric conversion element]
A 4 mm square metal mask is attached to the photoelectric conversion element, a solar simulator with an air mass (AM) of 1.5 G and an irradiance of 100 mW / cm ² is used as an irradiation light source, and an ITO electrode is connected with a source meter (Keisley, Model 2400). The current-voltage characteristic between the aluminum electrode was measured. By the above measurement, open circuit voltage Voc [V], short circuit current density Jsc [mA / cm ² ], form factor FF, and photoelectric conversion efficiency PCE [%] can be measured.

Here, the open circuit voltage Voc is the voltage value (V) when the current value = 0 (mA / cm ² ), and the short circuit current density Jsc is the current density (mA / cm ² ) when the voltage value = 0 (V). ). The form factor (FF) is a factor representing the internal resistance, and is represented by the following expression when the maximum output point is Pmax.
FF = Pmax / (Voc × Jsc)
Further, the photoelectric conversion efficiency PCE is given by the following equation when the incident energy is Pin.
PCE = Pmax / Pin = Voc × Jsc × FF / Pin

<Example 1>
[Synthesis of various copolymers]

<Synthesis Example 1>
[Synthesis of Imidothiophene Monomer 1]

  To a 500 mL eggplant flask, 5.3 g (30.7 mmol) of thiophene dicarboxylic acid and 100 mL of acetic anhydride were added and heated at 140 ° C. for 6 hours. The solvent was removed by distillation under reduced pressure, and recrystallization was performed with toluene to obtain 3.5 g of 1H, 3H-thieno [3,4-c] furan-1,3-dione.

  Under nitrogen, 3.57 g (0.023 mol) of 1H, 3H-thieno [3,4-c] furan-1,3-dione was dissolved in 35 mL of dehydrated DMF in a 100 mL eggplant flask. Then, 4.2 mL (0.025 mol) of n-octylamine was added in an ice bath and heated at 140 ° C. for 2 hours. The skin-colored powder which was mixed with water after standing to cool and collected was collected by filtration and washed with cold methanol to obtain 5.3 g of 4-[[1-octylamino] carbonyl] -3-thienophenecarboxylic acid.

4-[[1-octylamino] carbonyl] -3-thienophenecarboxylic acid 5.27 g (18.6 mmol) and thionyl chloride 18 mL were added to a 100 mL eggplant flask and the bath temperature was set to 72 ° C. and heated for 3 hours. After allowing to cool, the mixture was added dropwise to a 1N aqueous sodium hydroxide solution, and the precipitated brown powder was collected by filtration. This was washed with cold methanol and dried to obtain 4.55 g of 5-octyl-4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione (yield 91%).

(Imidothiophene monomer 1)
Under nitrogen, 5-octyl-4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione (2.65 g, 10 mmol) was dissolved in 50 mL of trifluoroacetic acid and 15 mL of concentrated sulfuric acid in a 200 mL eggplant flask. did. The mixture was further stirred in an ice bath until 5.33 g (30 mmol) of NBS was dissolved, then the ice bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 20 hours. After quenching by mixing with ice water, extraction was performed using chloroform, the solvent was removed by distillation under reduced pressure, and the residue was purified by column chromatography (developing solvent hexane: chloroform 2: 1 → 1: 1). After suspension washing with hexane, 2.58 g of imidothiophene monomer 1 (1,3-dibromo-5-octyl-4H-thieno [3,4-c] pyrrole-4,6- (5H) -dione) was obtained. Obtained (yield 61%).

<Synthesis Example 2>
[Synthesis of Dithienosilol Monomer 1]

(Dithienosilol monomer 1)
Add 0.1 g of 4,4′-dioctyl-5,5-dibromo-dithiono [3,2-b: 2 ′, 3′-d] silole to a 50 mL multi-necked flask, and use a vacuum pump and a drier. Nitrogen replacement was performed. After adding 5 mL of dehydrated THF and cooling the system in a dry ice-acetone bath, 0.28 mL of nBuLi in hexane solution was added and stirred for 15 minutes. Thereafter, 105 mg of trimethyltin chloride was added and the mixture was raised to room temperature and stirred for 2 hours. Quenched with water, extracted with hexane, dried over sodium sulfate, removed the solvent by distillation under reduced pressure, dithienosilol monomer 1 (4,4'-dioctyl-5,5-bis (trimethyltin)- dithiono [3,2-b: 2 ′, 3′-d] silole, green oil) 125 mg.

<Synthesis Example 3>
[Synthesis of Copolymer A]

(Copolymer A)
In a 50 mL eggplant flask under nitrogen, the imide thiophene monomer 1: 187 mg obtained in Synthesis Example 1 (1,3-dibromo-5-octyl-4H-thieno [3,4-c] pyrrole-4,6- (5H) -Dione, 0.443 mmol), dithienosilol monomer obtained in Synthesis Example 2 1: 340 mg (4,4′-dioctyl-5,5-bis (trimethyltin) -dithieno [3,2-b: 2 ′, 3′-d] silole, 0.443 mmol), tetrakis (triphenylphosphine) palladium (valent 0) 15 mg (0.013 mmol), copper (II) oxide 35 mg (0.443 mmol), toluene 6.75 mL and DMF 1.62 mL And stirred at 100 ° C. for 20 hours. Then, as a terminal treatment, 0.1 mL of bromobenzene was added and the mixture was stirred for 3 hours with heating. Further, 0.1 mL of trimethyl (phenyl) tin was added and stirred for 3 hours with heating, and the reaction solution diluted 5-fold with toluene was added dropwise to 400 mL of methanol. did. The precipitated copolymer was collected by filtration and purified using silica gel to obtain the desired copolymer A. Using a JAL908-C60 apparatus (Nippon Analytical Industrial) equipped with JAIGEL-3H (40φ), 2H (40φ), a developing solution: chloroform, a chloroform solution of a crude polymer (50-100 mg) under a flow rate of 14 mL / min ( 10 mL) and preparative purification was performed.
The weight average molecular weight, number average molecular weight and PDI of the fractionated copolymer A (hereinafter referred to as copolymer A1) were 5.5 × 10 ⁴ , 4.1 × 10 ⁴ and 1.34, respectively. When elemental analysis of the copolymer A1 was performed, the respective element amounts were Br: 90 ppm, Pd: 25 ppm, and Sn: 67 ppm.
Further, by carrying out the reaction according to the same method, copolymer A having a weight average molecular weight, a number average molecular weight and PDI of 4.4 × 10 ⁴ , 2.8 × 10 ⁴ and 1.50, respectively (hereinafter referred to as copolymer A2 and And a copolymer A (hereinafter referred to as a copolymer A3) having a weight average molecular weight, a number average molecular weight and a PDI of 1.9 × 10 ⁴ , 1.8 × 10 ⁴ and 1.08, respectively. When elemental analysis of the copolymer A2 was performed, the respective element amounts were Br: 170 ppm, Pd: 3.2 ppm, and Sn: 600 ppm.

<Synthesis Example 4>
[Synthesis of Dithienosilol Monomer 2]

(Dithienosilol monomer 2)
In Synthesis Example 2, instead of 4,4′-dioctyl-5,5-dibromo-dithiono [3,2-b: 2 ′, 3′-d] silole, 4,4′-di-n-octyl- Dithienosilole monomer 2 (4,4′-di-) was used in the same manner except that 5,5-dibromo-dithiono [3,2-b: 2 ′, 3′-d] silole (manufactured by Lumtec) was used. n-octyl-5,5-bis (trimethyltin) -dithiono [3,2-b: 2 ′, 3′-d] silole) was synthesized.

<Synthesis Example 5>
[Synthesis of Imidothiophene Monomer 2]

(Imidothiophene monomer 2)
In Synthesis Example 1, imidothiophene monomer 2 (1,3-dibromo-5- (3,5-bis () was used in the same manner except that 3,5-bistrifluoromethylphenylamine was used instead of n octylamine. trifluoromethyl) phenyl) -4H-thieno [3,4-c] pyrrole-4,6- (5H) -dione) was synthesized.

<Synthesis Example 6>
[Synthesis of Copolymer B]

(Copolymer B)
In Synthesis Example 3, dithienosilole monomer 1 (4,4′-dioctyl-5,5-bis (trimethyltin) -dithieno [3,2-b: 2 ′, 3′-d] obtained in Synthesis Example 2 dithienosilole monomer 2 (4,4′-di-n-octyl-5,5-bis (trimethyltin) -dithieno [3,2-b: 2 ′, Copolymer B was synthesized in the same manner except that 3′-d] silole) was used. The weight average molecular weight, number average molecular weight and PDI of the synthesized copolymer B were 2.8 × 10 ⁴ , 3.5 × 10 ³ and 7.87, respectively.

<Synthesis Example 7>
[Synthesis of Copolymer C]

(Copolymer C)
Copolymer C was synthesized in the same manner as in Synthesis Example 6 except that imidothiophene monomer 2 was used instead of imidothiophene monomer 1. The weight average molecular weight, number average molecular weight and PDI of the synthesized copolymer C were 4.7 × 10 ⁴ , 3.3 × 10 ⁴ and 1.42, respectively. When elemental analysis of the copolymer C was performed, the respective element amounts were Br: 190 ppm, Pd: 750 ppm, and Sn: 3600 ppm.

<Measurement of absorption spectrum>
The results of measuring the absorption spectra of various copolymers (copolymer A1, copolymer A2, copolymer A3, copolymer B and copolymer C) in chloroform are shown in FIGS. From the results of FIG. 4, it can be seen that the absorbance at 650 to 700 nm of the absorption spectrum was improved by the molecular weight being 2 × 10 ⁴ or more. An increase in absorbance at 650 to 700 nm in the absorption spectrum means that light having a wider range of wavelengths can be absorbed. Therefore, conversion efficiency is improved in a photoelectric conversion element including a copolymer having a molecular weight of 2 × 10 ⁴ or more in an active layer. Is expected to do.

In addition, the copolymer (copolymer B) in which the substituents (R ³ and R ⁴ ) bonded to Si of the dithienosilol skeleton are linear alkyl groups is the same as the copolymer (copolymer A2) in which the substituent is a linear alkyl group. In comparison, it can be seen that the longest end of the absorption spectrum is increased to a wavelength near 720 nm and the absorbance at 400 to 600 nm is improved. The fact that the copolymer can absorb more light of a long wavelength and that the absorption characteristics at 400 to 600 nm are improved means that it can absorb light of a wider wavelength. Therefore, in a photoelectric conversion element including such a copolymer in an active layer. The conversion efficiency is expected to improve.

From the results of FIG. 5, the copolymer substituents attached to the nitrogen atom of the imide thiophene skeleton (R ¹⁾ is an aryl group (copolymer C), said substituent (R ¹⁾ is a straight-chain alkyl group It was found that both the absorption maximum wavelength and the longest end of the absorption spectrum become longer than that of a certain copolymer (copolymer A2). The ability of the copolymer to absorb more light having a longer wavelength means that light having a wider wavelength can be absorbed. Therefore, it is expected that the conversion efficiency is improved in a photoelectric conversion element including such a copolymer in the active layer.

<Example 2>
[Photoelectric conversion element using copolymer A1]
[Preparation of organic active layer coating solution S0]
The weight ratio of the copolymer A1 having a weight average molecular weight of 5.5 × 10 ⁴ obtained in Synthesis Example 3 that is a p-type semiconductor material and PC71BM (NS-E112 manufactured by Frontier Carbon Corporation) that is an n-type semiconductor material is The mixture was mixed at 1: 1.5 and dissolved in chlorobenzene in a nitrogen atmosphere so that the mixture had a concentration of 1.0% by weight. Next, 1,8-diiodooctane was added to this solution so that the ratio was 3.2% by weight with respect to the whole coating solution of the organic active layer, and the mixture was stirred and mixed at 80 ° C. for 4 hours using a hot stirrer. . The solution after stirring and mixing was filtered through a 0.45 μm polytetrafluoroethylene (PTFE) filter to obtain an organic active layer coating solution S0.

[Production of photoelectric conversion element]
A glass substrate patterned with an indium tin oxide (ITO) transparent conductive film is cleaned in the order of ultrasonic cleaning with a surfactant, water with ultrapure water, and ultrasonic cleaning with ultrapure water, and then dried with nitrogen blow. I let you.
Finally, ultraviolet ozone cleaning was performed on the substrate. On this substrate, a poly (3,4-ethylenedioxythiophene) poly (styrenesulfonic acid) aqueous dispersion (“CLVIOSTMs PVP AI4083” manufactured by H.C. The substrate was coated by spin coating under the conditions, and the substrate after coating was heated in the air on a hot plate at 120 ° C. for 10 minutes. The film thickness of the hole extraction layer was about 30 nm.

  The substrate on which the hole extraction layer was formed was heat-treated at 220 ° C. for 3 minutes on a hot plate in a glove box in a nitrogen atmosphere. After the substrate was cooled, the organic active layer coating solution S0 produced as described above was spin-coated at a speed of 230 rpm to form an organic active layer having a thickness of about 100 nm. Thereafter, lithium fluoride with a thickness of 0.6 nm as an electron extraction layer and aluminum with a thickness of 80 nm as an electrode were sequentially formed by resistance heating vacuum deposition to produce a 5 mm square photoelectric conversion element.

[Evaluation of photoelectric conversion element]
The current-voltage characteristics of the produced photoelectric conversion element were measured. Table 1 shows the measurement results of each parameter of the open circuit voltage Voc [V], the short circuit current density Jsc [mA / cm ² ], the form factor FF, and the photoelectric conversion efficiency PCE [%].

<Example 3>
[Photoelectric conversion element using copolymer A2]
In Example 2, instead of the copolymer A1 having a weight average molecular weight of 5.5 × 10 ⁴ , the copolymer A2 having a weight average molecular weight of 4.4 × 10 ⁴ described in Synthesis Example 3 was used, and fluorination was performed as an electron extraction layer. A 5 mm square photoelectric conversion element was used in the same manner except that POPy ₂ obtained according to Synthesis Example 8 shown below was used instead of lithium and the thickness of the electron extraction layer was changed from 0.6 nm to 2.5 nm. Was made. Table 1 shows the measurement results of the current-voltage characteristics.

<Synthesis Example 8>
[Synthesis example of POPy ₂ ]

  In a nitrogen atmosphere, 1-bromopyrene (Tokyo Kasei Co., Ltd .: 14 g, 50 mmol) was dissolved in dehydrated THF (Kanto Chemical Co., Ltd .: 200 mL), cooled to −78 ° C., and then n-BuLi (Kanto Chemical: 33 mL, 1 6M) was slowly added dropwise, and the mixture was stirred for 30 minutes while maintaining -78 ° C. Subsequently, dichlorophenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd .: 4.3 g, 9.0 mmol) was added dropwise, and after sufficient stirring, the mixture was warmed to room temperature and stirred for 1.5 h. 30 mL of methanol (manufactured by Junsei Co., Ltd.) was added to the obtained reaction solution, and the resulting crude purified product was filtered and recrystallized using benzene to obtain 10.7 g of the desired product.

The compound obtained here was dissolved in 350 mL of THF (manufactured by Junsei Chemical Co., Ltd.), 300 mL of CH ₂ Cl ₂ (manufactured by Kanto Chemical Co., Ltd.), and 100 mL of acetone (manufactured by Kanto Chemical Co., Ltd.) 30% by weight solution (10 mL) was added and stirred at room temperature for 30 minutes. The reaction solution was added with 30 mL of water, concentrated to 600 mL, and then filtered to obtain 7.5 g of the desired product (POPy ₂ ).

<Example 4>
[Photoelectric conversion element using copolymer A2]
In Example 3, using the BINAPO obtained according to Synthesis Example 9 below in place of Popy ₂ as an electron extraction layer, except that the thickness of the electron extraction layer was changed from 2.5nm to 5nm, similarly A 5 mm square photoelectric conversion element was produced. Table 1 shows the measurement results of the current-voltage characteristics.

<Synthesis Example 9>
[Synthesis example of BINAPO]

  To a solution of BINAP (Wako Pure Chemical: 1.86 g, 3 mmol) in tetrahydrofuran (80 mL) was added 30 wt% aqueous hydrogen peroxide (Wako Pure Chemical: 3 mL), and the mixture was stirred for 2.5 hours. Then, 20 mL of water was added, tetrahydrofuran was distilled off under reduced pressure, and the obtained crude product was washed with methanol and filtered to obtain the target product BINAPO (1.78 g, 2.7 mmol) in a yield of 91%.

<Example 5>
[Photoelectric conversion element using copolymer A2]
In Example 4, a 5 mm square photoelectric conversion element was produced in the same manner except that F-POPy ₂ obtained according to Synthesis Example 10 shown below was used instead of BINAPO as the electron extraction layer. Table 1 shows the measurement results of the current-voltage characteristics.

<Synthesis Example 10>
[Synthesis Example of F-POPy ₂ ]

  Under a nitrogen atmosphere, 1-bromopyrene (Tokyo Kasei: 5.6 g, 20 mmol) was dissolved in dehydrated tetrahydrofuran (Kanto Chemical: 100 mL), cooled to −78 ° C., and then n-butyllithium (Kanto Chemical: 13 mL, 1. 6M) was slowly added dropwise and stirred for 45 minutes while maintaining -78 ° C. Subsequently, triphenyl phosphite (Wako Pure Chemicals: 3.1 g, 10 mmol) was added dropwise, and after sufficient stirring, the temperature was raised to room temperature, further stirred for 1.5 h, and then cooled to -78 ° C again. On the other hand, 4-fluorobromobenzene (Tokyo Kasei: 3.5 g, 20 mmol) was dissolved in dehydrated tetrahydrofuran (50 mL) in a separate reaction vessel, and n-butyllithium (Kanto Chemical: 13 mL, 1.6 M) was added, and the mixture was stirred for 30 minutes, then dropped in the first container, warmed to room temperature, and further stirred for 1 hour.

20 mL of water was added to the obtained reaction solution, tetrahydrofuran was distilled off under reduced pressure, and extraction was performed using methylene chloride. Magnesium sulfate was added to the organic layer, dried, filtered and concentrated, and purified by column chromatography (developing solvent: hexane) to obtain 3.7 g of the desired product. The compound obtained here was dissolved in acetone (Kanto Chemical Co., Inc .: 150 mL), hydrogen peroxide water (Wako Pure Chemicals: 2 mL of 30 wt% solution) was added, and the mixture was stirred at room temperature. After adding 20 mL of water to the reaction solution, the mixture was concentrated and washed with acetonitrile to obtain 1.9 g of the desired product (F-POPy ₂ ).

<Example 6>
[Photoelectric conversion element using copolymer A2]
In Example 4, a 5 mm square photoelectric conversion element was produced in the same manner except that (CF ₃ ) ₂ -POPy ₂ obtained according to Synthesis Example 11 shown below was used instead of BINAPO as the electron extraction layer. . Table 1 shows the measurement results of the current-voltage characteristics.

<Synthesis Example 11>
[Synthesis Example of (CF ₃ ) ₂ -POPy ₂ ]

  In a nitrogen atmosphere, 1-bromopyrene (Tokyo Kasei: 5.6 g, 20 mmol) was dissolved in dehydrated tetrahydrofuran (Kanto Chemical: 100 mL), cooled to −78 ° C., and then n-BuLi (Kanto Chemical: 13 mL, 1.6 M). ) Was slowly added dropwise and stirred for 30 minutes while maintaining -78 ° C. Subsequently, triphenyl phosphite (Wako Pure Chemicals: 3.1 g, 10 mmol) was added dropwise, and after sufficient stirring, the temperature was raised to room temperature, stirred for 1.5 hours, and cooled to -78 ° C again.

  On the other hand, 3,5-bistrifluoromethylbromobenzene (Tokyo Kasei: 5.8 g, 20 mmol) was dissolved in dehydrated tetrahydrofuran (50 mL) in a separate reaction vessel, and n-butyl in a nitrogen atmosphere at −78 ° C. Lithium (Kanto Chemical: 13 mL, 1.6 M) was added and stirred for 30 minutes, then dropped in the first container, warmed to room temperature, and stirred for 12 hours. 20 mL of water was added to the obtained reaction solution, tetrahydrofuran was distilled off under reduced pressure, and extraction was performed using dichloromethane. Magnesium sulfate was added to the organic layer, dried, concentrated by filtration, and purified by column chromatography (developing solvent: mixed solvent of hexane / dichloromethane) to obtain 0.9 g of a target product precursor. The compound was identified using NMR.

0.9 g of the compound obtained above was dissolved in dichloromethane (Kanto Chemical: 100 mL), hydrogen peroxide solution (Wako Pure Chemicals: 2% of 30% solution) was added, and the mixture was stirred at room temperature. 20 mL of water was added to the reaction solution, the product was extracted, dried using sodium sulfate, and the solvent was removed by distillation under reduced pressure. The suspension was washed with hexane and methanol to obtain 0.6 g (yield 9%) of the desired product ((CF ₃ ) ₂ -POPy ₂ ). The resulting product was confirmed by NMR.

<Comparative Example 1>
[Photoelectric conversion element using PBDTTPD]
[Preparation of organic active layer coating solution S1]
PBDTTPD obtained in Synthesis Example 12 shown below, which is a p-type semiconductor material, and PC71BM (NS-E112 manufactured by Frontier Carbon Corporation), which is an n-type semiconductor material, are mixed so that the weight ratio is 1: 1.5. Then, the mixture was dissolved in chlorobenzene in a nitrogen atmosphere so as to have a concentration of 0.8% by weight. Next, 1,8-diiodooctane was added to this solution so that the ratio was 2.0% by weight with respect to the whole coating solution of the organic active layer, and the mixture was stirred at a temperature of 80 ° C. for 4 hours using a hot stirrer. Mixed. The solution after stirring and mixing was filtered through a 0.45 μm polytetrafluoroethylene (PTFE) filter to obtain an organic active layer coating solution S1.

[Production and evaluation of photoelectric conversion elements]
Using the organic active layer coating solution S1 instead of the organic active layer coating solution S0, a photoelectric conversion element was produced in the same manner as in Example 2 described above, and the current-voltage characteristics of the produced photoelectric conversion element were measured. The spin coating condition for the organic active layer was 300 rpm, and the thickness of the organic active layer was about 100 nm. Table 1 shows the measurement results of the current-voltage characteristics.

<Synthesis Example 12>
[Synthesis of PBDTTPD]

(PBDTTPD)
Poly (2,6- (4,8-bis (2-ethylhexyloxy) benzo [1,2-b: 4,5-b '] dithiophene))-alt- (5-octyl-4H-thieno [3,4 -C] pyrrole-4,6 (5H) -dione-1,3-diyl) (PBDTTPD) Am. Chem. Soc. 2010, 132, 7595-7597, and the synthesis was performed.

<Comparative example 2>
[Photoelectric conversion element using PDTSBT]
[Preparation of organic active layer coating solution S2]
The PDTSBT obtained in Synthesis Example 13 shown below, which is a p-type semiconductor material, and PC71BM (NS-E112, manufactured by Frontier Carbon Co.), which is an n-type semiconductor material, are mixed so that the weight ratio is 1: 1. The mixture was dissolved in chlorobenzene in a nitrogen atmosphere so as to have a concentration of 1.0% by weight. Next, 1,8-diiodooctane was added to this solution so that the ratio was 3.2% by weight with respect to the whole coating solution of the organic active layer, and the mixture was stirred at a temperature of 80 ° C. for 4 hours using a hot stirrer. Mixed. The solution after stirring and mixing was filtered through a 1.0 μm polytetrafluoroethylene (PTFE) filter to obtain an organic active layer coating solution S2.

[Production and evaluation of photoelectric conversion elements]
Using the organic active layer coating solution S2 instead of the organic active layer coating solution S0, a photoelectric conversion element was produced in the same manner as in Example 2 described above, and the current-voltage characteristics of the produced photoelectric conversion element were measured. The spin coating condition of the organic active layer was 500 rpm, and the thickness of the organic active layer was about 80 nm. Table 1 shows the measurement results of the current-voltage characteristics.

<Synthesis Example 13>
[Synthesis of PDTSBT]

(PDTSBT)
Poly (2,6- (4,4-bis (2-ethylhexyl) 4H-silolo [3,2-b: 4,5-b '] dithiophene) -alt- (benzo [c] [1,2,5 ] Thiadiazole-4,7-diyl)) (PDTSBT) was synthesized with reference to the description of WO2010 / 022058.

  As shown in Table 1, in Examples 2 to 6, by using an organic semiconductor material containing a copolymer containing an imidothiophene skeleton and a dithienosilole skeleton, photoelectric conversion characteristics significantly higher than those of Comparative Examples 1 and 2 were obtained.

[Measurement of LUMO and Glass Transition Temperature (Tg) of Electron Extraction Layer Material]
The LUMO and glass transition temperature (Tg) of various electron extraction layer materials were measured by the methods described above. The results are shown in Table 2.

  From the results of Tables 1 and 2, it was found that the photoelectric conversion efficiency is improved by using a compound having a LUMO of the material of the electron extraction layer in a specific range. Moreover, it turns out that photoelectric conversion efficiency improves by using the compound whose glass transition temperature (Tg) exists in a specific range, and it is anticipated that the durability of an element improves.

[Measurement of X-ray diffraction]
The X-ray diffraction spectrum of copolymer A2 is shown in FIG. A diffraction peak (2θ = 4.77 °) was detected. When the interplanar spacing (d) was calculated from this peak value, d = 1.85 nm. A thiophene oligomer typified by P3HT has a two-dimensional laminated lamella structure in which the arrangement of molecules is promoted and densely stacked, and a diffraction peak corresponding to a plane spacing of d = 1.6 nm is observed. In view of this, the copolymer A2 is also considered to be a crystalline material having a laminated structure in which molecules are arranged.

  From the above, since the copolymer of the present invention can be formed by a practical coating process and has light absorption at a long wavelength, the photoelectric conversion element to which the present polymer is applied has a high open-circuit voltage and conversion efficiency and / or Since it is excellent in durability, it was confirmed that it can be used for solar cells and the like.

DESCRIPTION OF SYMBOLS 1 Weather-resistant protective film 2 UV cut film 3,9 Gas barrier film 4,8 Getter material film 5,7 Sealing material 6 Solar cell element 10 Back sheet 12 Base material 13 Solar cell module 14 Thin film solar cell 101 Anode 102 Hole extraction Layer 103 Active layer (mixed layer of p-type semiconductor compound and n-type semiconductor compound)
104 Electron extraction layer 105 Cathode 106 Substrate 107 Photoelectric conversion element

Claims (8)

A copolymer having a repeating unit represented by the following general formula (1), having a polystyrene-equivalent weight average molecular weight of 2 × 10 ⁴ or more and 1 × 10 ⁷ or less.
(In the formula (1), R ¹ represents a substituent alkyl group which may have a which may have an optionally substituted alkenyl group or an optionally substituted aryl group, R ² to R ⁵ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, which may have an optionally substituted alkenyl group or an optionally substituted aryl group Represents.)   An organic semiconductor material comprising the copolymer of claim 1.   An organic electronic device comprising the organic semiconductor material according to claim 2.   A photoelectric conversion element comprising an organic active layer disposed between a pair of electrodes, wherein the organic active layer includes the organic semiconductor material according to claim 2.   The organic semiconductor material comprises a fullerene compound, a borane derivative, a thiazole derivative, a benzothiazole derivative, a benzothiadiazole derivative, an N-alkyl-substituted naphthalenetetracarboxylic acid diimide, an N-alkyl-substituted perylene diimide derivative, and an n-type polymer. The photoelectric conversion element according to claim 4, comprising at least one n-type semiconductor compound selected from the group.   Furthermore, the photoelectric conversion element of Claim 4 or 5 which has a buffer layer containing the phosphine compound which has a group 16 element and a double bond.   The photoelectric conversion element according to claim 4, wherein the photoelectric conversion element is a solar battery.   A solar cell module comprising the photoelectric conversion element according to claim 7.