JP5822117B2 - Photoelectric conversion element, method for producing fullerene compound, and fullerene compound - Google Patents

Description

  The present invention relates to a photoelectric conversion element, a method for producing a fullerene compound, and a fullerene compound. In particular, the present invention relates to an organic photoelectric conversion element suitable for use in an organic solar battery.

Fullerene is used as an n-type semiconductor compound for organic thin-film solar cells. In particular, fullerene compounds having an additional group are attracting attention because coating film formation becomes easy. The fullerene compound having an addition group, known as methanofullerene derivative _{[6,6] -Phenyl-C 61 -Butyric} Acid Methyl Ester ( phenyl _{C 61} butyric acid methyl ester, PCBM) has been generally used (Patent Document 1, Non-Patent Document 1).

  Patent Document 1 discloses the use of bisPCBM having two additional groups as means for further improving the performance of a photoelectric conversion element using PCBM, and the level of the lowest unoccupied molecular orbital (LUMO) of the fullerene compound is disclosed. As a result of the increase, the open circuit voltage (Voc) is improved, and as a result, the efficiency is improved.

Further, an organic thin film solar cell using a fullerene compound (C ₆₀ (Ind) ₂ ) added with two indenes as an n-type semiconductor compound and a P3HT conjugated polymer as a p-type semiconductor compound has a photoelectric conversion of 5% or more. It has been reported to show efficiency (Patent Document 2). Also in this case, as in the case of bisPCBM, a high open-circuit voltage (Voc) is achieved by using a plurality of additional groups.

International Publication No. 2009/039490 International Publication No. 2008/018931

Adv. Funct. Mater. 2009, 19, 779-788

Even in the photoelectric conversion element using bisPCBM described in Patent Document 1, the photoelectric conversion efficiency was not sufficient. Even when the fullerene compound (C ₆₀ (Ind) ₂ ) added with indene used in Patent Document 2 is used, its photoelectric conversion efficiency and durability are not always sufficient, and further improvement is desired.

  The present invention includes a method for efficiently producing a dihydromethano group-added fullerene compound that can be used as a material for a photoelectric conversion element having excellent photoelectric conversion efficiency, the dihydromethano group-added fullerene compound, and the dihydromethano group-added fullerene compound. An object of the present invention is to provide a photoelectric conversion element.

  The inventors of the present application replace a part of the plurality of additional groups of the fullerene compound with a dihydromethano group having a small steric hindrance, thereby suppressing the steric hindrance while maintaining the LUMO level at a high position. We thought that the photoelectric conversion efficiency could be improved. Therefore, it was planned to develop various fullerene compounds having a dihydromethano group and use them in the active layer to develop a photoelectric conversion element exhibiting high photoelectric conversion efficiency.

  However, a method for efficiently adding a dihydromethano group to fullerene has not yet been established, and the yield is low, purification is difficult, or it is not necessarily suitable for synthesis and industrialization on a large scale. (For example, JP-A-7-187627, J. Am. Chem. Soc. 1993, 115, 5829-5830., Chem. Commun, 1996, 1547-1548., Chem. Commun, 2000, 1065-1066. Tetrahedron Lett. 2003, 5473-5476.). Therefore, in order to develop a photoelectric conversion device using a fullerene compound having a dihydromethano group, it is necessary to find a highly efficient method for producing a dihydromethano group-added fullerene compound.

  The inventors of the present application have studied in view of the above-described conventional situation, and as a result, have found a highly efficient method for producing a dihydromethano group-added fullerene compound. Moreover, the dihydromethano group addition fullerene compound suitable for use for a photoelectric conversion element was discovered, and also the photoelectric conversion element using this was discovered, and it came to achieve this invention.

上式（ｎ１）乃至（ｎ７）において、ＦＬＮはフラーレンを表す。前記有機基が結合するフラーレン上の炭素原子は、フラーレン骨格中の同一の五員環若しくは六員環に位置する。ｒ，ｓ，ｔ，ｕ，ｖ，ｗ，ｘは独立した０以上の整数であり、ｒ，ｓ，ｔ，ｕ，ｖ，ｗ，及びｘの合計は１以上５以下である。
式（ｎ１）中、Ｌは１以上８以下の整数であり、Ｒ^１は置換基を有していても良い炭素数１〜１４のアルキル基、置換基を有していても良い炭素数１〜１４のアルコキシ基、又は置換基を有していても良い芳香族基であり、Ｒ^２乃至Ｒ^４は各々独立して、水素原子、炭素数１〜１４のアルキル基、炭素数１〜１４のフッ化アルキル基、又は置換基を有していても良い芳香族基である。
式（ｎ２）中、Ｒ^５乃至Ｒ^９は各々独立に、水素原子、置換基を有していても良い炭素数１〜１４のアルキル基、又は置換基を有していても良い芳香族基である。
式（ｎ３）中、Ａｒ^１は、置換基を有していても良い炭素数６〜２０の芳香族炭化水素基または炭素数２〜２０の芳香族複素環基であり、Ｒ^１０乃至Ｒ^１３は各々独立して、水素原子、置換基を有していても良いアルキル基、置換基を有していても良いアミノ基、置換基を有していても良いアルコキシ基、または置換基を有していても良いアルキルチオ基である。Ｒ^１０若しくはＲ^１１は、Ｒ^１２若しくはＲ^１３と環を形成しても良い。
式（ｎ４）中、Ｒ^１４とＲ^１５との一方は水素原子、アルコキシカルボニル基、置換基を有していても良い炭素数１〜１４のアルキル基、又は置換基を有していても良い芳香族基であり、他方はアルコキシカルボニル基、置換基を有していても良い炭素数１〜１４のアルキル基、又は置換基を有していても良い芳香族基である。
式（ｎ５）中、Ａｒ^２及びＡｒ^３は各々独立して、置換基を有していても良い炭素数６〜２０の芳香族炭化水素基あるいは置換基を有していても良い炭素数２〜２０の芳香族複素環基である。
式（ｎ６）中、Ａｒ^４及びＡｒ^５は各々独立して、置換基を有していても良い炭素数６〜２０の芳香族炭化水素基あるいは置換基を有していても良い炭素数２〜２０の芳香族複素環基である。
式（ｎ７）中、Ｒ^１６及びＲ^１７は各々独立して、置換基を有していても良い炭素数１〜１４のアルキル基、あるいは置換基を有していても良い芳香族基である。 That is, the gist of the present invention is as follows.
A photoelectric conversion element comprising at least a pair of electrodes and an active layer, wherein the active layer contains a fullerene compound substituted with one or more dihydromethano groups and one or more organic groups, A photoelectric conversion element comprising one or more organic groups represented by the following formulas (n1) to (n7):

In the above formulas (n1) to (n7), FLN represents fullerene. The carbon atom on the fullerene to which the organic group is bonded is located in the same 5-membered ring or 6-membered ring in the fullerene skeleton. r, s, t, u, v, w, and x are independent integers of 0 or more, and the sum of r, s, t, u, v, w, and x is 1 or more and 5 or less.
In the formula (n1), L is an integer of 1 to 8, and R ¹ is an alkyl group having 1 to 14 carbon atoms that may have a substituent, and 1 carbon atom that may have a substituent. -14 alkoxy group or an aromatic group which may have a substituent, R ^{2 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or 1 to 14 carbon atoms. The fluorinated alkyl group or an aromatic group which may have a substituent.
In formula (n2), R ^{5 to} R ⁹ 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.
In formula (n3), Ar ¹ is an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 2 to 20 carbon atoms, and R ^{10 to} R ^13. Each independently has a hydrogen atom, an alkyl group which may have a substituent, an amino group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An alkylthio group which may be used. R ¹⁰ or R ¹¹ may form a ring with R ¹² or R ¹³ .
In formula (n4), one of R ¹⁴ and R ¹⁵ may have a hydrogen atom, an alkoxycarbonyl group, an alkyl group having 1 to 14 carbon atoms which may have a substituent, or a substituent. The other is an aromatic group, and the other is an alkoxycarbonyl group, an alkyl group having 1 to 14 carbon atoms which may have a substituent, or an aromatic group which may have a substituent.
In the formula (n5), Ar ² and Ar ³ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or 2 carbon atoms which may have a substituent. -20 aromatic heterocyclic groups.
In the formula (n6), Ar ⁴ and Ar ⁵ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or 2 carbon atoms which may have a substituent. -20 aromatic heterocyclic groups.
In formula (n7), R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 14 carbon atoms which may have a substituent, or an aromatic group which may have a substituent. .

  Method for efficiently producing a dihydromethano group-added fullerene compound that can be used as a material for a photoelectric conversion device having excellent photoelectric conversion efficiency, the dihydromethano group-added fullerene compound, and a photoelectric conversion device containing the dihydromethano group-added fullerene compound Can provide.

The figure which shows the photoelectric conversion element which concerns on one Embodiment of this invention. The figure which shows the solar cell which concerns on one Embodiment of this invention. The figure which shows the solar cell which concerns on one Embodiment of this invention.

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

<1. Photoelectric conversion element>
The photoelectric conversion element according to the present invention has at least one pair of electrodes and an active layer disposed between the electrodes. The active layer contains a dihydromethano group-added fullerene compound described below. Below, one Embodiment of the photoelectric conversion element which concerns on this invention is described. In FIG. 1, the photoelectric conversion element 100 which is one Embodiment of this invention is shown. FIG. 1 shows a photoelectric conversion element used in a general organic thin film solar cell, but the photoelectric conversion element according to the present invention is not limited to the structure of FIG. The photoelectric conversion element 100 according to FIG. 1 includes electrodes 120 and 160 and an active layer 140. Furthermore, the photoelectric conversion element according to the present embodiment may include a substrate 110 and buffer layers 130 and 150 as shown in FIG. In FIG. 1, the electrode 120 is a positive electrode and the electrode 160 is a negative electrode. Of course, in other embodiments of the present invention, the positive and negative electrodes may be reversed. Hereinafter, each of these parts will be described.

<1.1 Active layer (140)>
In the photoelectric conversion element 100 according to this embodiment, the active layer 140 includes a p-type semiconductor compound and an n-type semiconductor compound. In the photoelectric conversion element, light is absorbed by the active layer, 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 electrode.

  The thickness of the active layer is not particularly limited, but the thickness of the active layer is preferably 10 to 1000 nm, more preferably 50 to 200 nm. When the thickness of the active layer is 10 nm or more, uniformity can be maintained and short circuit is hardly caused. In addition, when the thickness of the active layer is 1000 nm or less, the internal resistance can be reduced, and further, the distance between the electrodes is close, so that the charge diffusion can be improved. Although the manufacturing method of an active layer is not specifically limited, For example, it can manufacture by apply | coating the solution which melt | dissolved the p-type semiconductor compound, the n-type semiconductor compound, or both using spin coating etc. It can also be produced by vapor-depositing a p-type semiconductor compound and an n-type semiconductor compound.

  The active layer is composed of a thin film stack type in which a p-type semiconductor compound and an n-type semiconductor compound are stacked, a bulk heterojunction type in which a p-type semiconductor compound and an n-type semiconductor compound are mixed, and a p-type semiconductor in an intermediate layer of the thin film stack type. Examples include a structure having a layer (i layer) in which a compound and an n-type semiconductor compound are mixed. In particular, when the p-type semiconductor compound is a polymer material, a bulk heterojunction type in which a p-type semiconductor compound and an n-type semiconductor compound are mixed is preferable. When the p-type semiconductor compound is a low-molecular material, a structure having a layer (i layer) in which a p-type semiconductor compound and an n-type semiconductor compound are mixed in a thin-film stacked intermediate layer, for example, a pin stack. The structure is preferable because the active layer capable of generating a photocurrent can be thickened.

[Thin film type active layer]
The thin film stacked active layer has a structure in which a p-type semiconductor layer containing a p-type semiconductor compound and an n-type semiconductor layer containing an n-type semiconductor compound are stacked. The thin film stacked active layer can be formed by forming a p-type semiconductor layer and an n-type semiconductor layer, respectively. The p-type semiconductor layer and the n-type semiconductor layer may be formed by different methods.

[P-type semiconductor layer]
The p-type semiconductor layer is a layer containing a p-type semiconductor compound described later. There is no limitation on the film thickness of the p-type semiconductor layer. However, it is usually 5 nm or more, preferably 10 nm or more, and usually 500 nm or less, preferably 200 nm or less. When the film thickness of the p-type semiconductor layer is 500 nm or less, it is preferable in that the series resistance is lowered. It is preferable that the thickness of the p-type semiconductor layer is 5 nm or more because more light can be absorbed.

  The p-type semiconductor layer can be formed by any method including a coating method and a vapor deposition method, but the use of the coating method is preferable in that the p-type semiconductor layer can be formed more easily. When a p-type semiconductor layer is produced by a coating method, a coating solution containing a p-type semiconductor compound may be prepared and applied. As an application method, any method can be used. For example, spin coating method, inkjet method, doctor blade method, drop casting method, reverse roll coating method, gravure coating method, kiss coating method, roll brush method, spray coating method , Air knife coating method, wire barber coating method, pipe doctor method, impregnation / coating method or curtain coating method. You may perform a drying process by heating etc. after application | coating of a coating liquid. As will be described later, after preparing a coating liquid containing a p-type semiconductor compound precursor and applying the coating liquid, the p-type semiconductor compound precursor is converted into a p-type semiconductor compound, whereby a p-type semiconductor layer is formed. May be formed.

[N-type semiconductor layer]
The n-type semiconductor layer is a layer containing an n-type semiconductor compound described later. Of the n-type semiconductor compounds, 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more is the dihydromethano group-added fullerene compound described later. Since the dihydromethano group-added fullerene compound described later has suitable properties as an n-type semiconductor compound, it is particularly preferable that the n-type semiconductor layer contains only the dihydromethano group-added fullerene compound described later as an n-type semiconductor compound. There is no limitation on the film thickness of the n-type semiconductor layer. However, it is usually 5 nm or more, preferably 10 nm or more, and usually 500 nm or less, preferably 200 nm or less. When the film thickness of the n-type semiconductor layer is 500 nm or less, it is preferable in that the series resistance is lowered. It is preferable that the thickness of the n-type semiconductor layer is 5 nm or more because more light can be absorbed.

  The n-type semiconductor layer can be formed by any method including a coating method and a vapor deposition method, but it is preferable to use the coating method because the n-type semiconductor layer can be more easily formed. When an n-type semiconductor layer is formed by a coating method, a coating solution containing an n-type semiconductor compound may be prepared and this coating solution may be applied. As a coating method, any method can be used, and for example, the methods mentioned as the method for forming the p-type semiconductor layer can be used. You may perform a drying process by heating etc. after application | coating of a coating liquid.

[Bulk heterojunction active layer]
The bulk heterojunction active layer has a layer (i layer) in which a p-type semiconductor compound described later and an n-type semiconductor compound described later are mixed. The i layer has a structure in which the p-type semiconductor compound and the n-type semiconductor compound are phase-separated, carrier separation occurs at the phase interface, and the generated carriers (holes and electrons) are transported to the electrode.

  Of the n-type semiconductor compounds contained in the i layer, 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more are dihydromethano group-added fullerene compounds described later. Since the dihydromethano group-added fullerene compound described later has suitable properties as an n-type semiconductor compound, it is particularly preferable that the i layer contains only the dihydromethano group-added fullerene compound described later as an n-type semiconductor compound.

  There is no restriction | limiting in the film thickness of i layer. However, it is usually 5 nm or more, preferably 10 nm or more, and usually 500 nm or less, preferably 200 nm or less. When the film thickness of the i layer is 500 nm or less, it is preferable in that the series resistance is lowered. When the film thickness of the i layer is 5 nm or more, it is preferable in that more light can be absorbed.

  The i layer can be formed by any method including a coating method and a vapor deposition method (for example, a co-evaporation method), but it is preferable to use the coating method because the i layer can be formed more easily. When the i layer is produced by a coating method, a coating solution containing a p-type semiconductor compound and an n-type semiconductor compound may be prepared, and this coating solution may be applied. The coating liquid containing the p-type semiconductor compound and the n-type semiconductor compound may be prepared by preparing and mixing a solution containing the p-type semiconductor compound and a solution containing the n-type semiconductor compound, respectively. It may be prepared by dissolving the compound and the n-type semiconductor compound. In addition, as will be described later, after preparing a coating liquid containing a p-type semiconductor compound precursor and an n-type semiconductor compound, and applying this coating liquid, converting the p-type semiconductor compound precursor into a p-type semiconductor compound. Thus, the i layer may be formed. As a coating method, any method can be used, and for example, the methods mentioned as the method for forming the p-type semiconductor layer can be used. You may perform a drying process by heating etc. after application | coating of a coating liquid.

  When the bulk heterojunction active layer is formed by a coating method, an additive may be further added to the coating solution containing the p-type semiconductor compound and the n-type semiconductor compound. The phase separation structure of the p-type semiconductor compound and the n-type semiconductor compound in the bulk heterojunction active layer has an effect on the light absorption process, exciton diffusion process, exciton separation (carrier separation) process, carrier transport process, etc. is there. Therefore, it is considered that good photoelectric conversion efficiency can be realized by optimizing the phase separation structure. When the coating solution contains an additive having volatility different from that of the solvent, a preferable phase separation structure can be obtained at the time of forming the organic active layer, and the photoelectric conversion efficiency can be improved. Therefore, the additive is preferably contained.

  As an example of an additive, the compound etc. which are described in the international publication 2008/066933 are mentioned, for example. More specific examples of the additive include an aliphatic hydrocarbon such as an alkane having a substituent or an aromatic compound such as naphthalene having a substituent. Examples of substituents include aldehyde groups, oxo groups, hydroxy groups, alkoxy groups, thiol groups, thioalkyl groups, carboxyl groups, ester groups, amine groups, amide groups, fluoro groups, chloro groups, bromo groups, iodo groups, halogen groups, A nitrile group, an epoxy group, an aromatic group, an arylalkyl group, etc. are mentioned. There may be one or more, for example two, substituents. A preferred substituent for the alkane is a thiol group or an iodo group. Moreover, as a substituent which an aromatic compound like naphthalene has, Preferably, they are a bromo group or a chloro group.

  Since the additive preferably has a high boiling point, the aliphatic hydrocarbon used as the additive preferably has 6 or more carbon atoms, and more preferably 8 or more carbon atoms. Moreover, since it is preferable that an additive is liquid at normal temperature, carbon number of an aliphatic hydrocarbon has preferable 14 or less, and 12 or less is more preferable. For the same reason, the aromatic hydrocarbon used as an additive usually has 6 or more carbon atoms, preferably 8 or more, more preferably 10 or more, and usually 50 or less, preferably 30 or less, more preferably 20 or less. The number of carbon atoms of the aromatic heterocycle used as an additive is usually 2 or more, preferably 3 or more, more preferably 6 or more, and usually 50 or less, preferably 30 or less, more preferably 20 or less. The boiling point of the additive is usually 100 ° C. or higher, preferably 200 ° C. or higher, and usually 600 ° C. or lower, preferably 500 ° C. or lower, at normal pressure (one atmospheric pressure).

  The amount of the additive contained in the coating solution containing the p-type semiconductor compound and the n-type semiconductor compound is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more with respect to the entire coating solution. Moreover, 10 weight% or less is preferable with respect to the whole coating liquid, and 3 weight% or less is more preferable. When the amount of the additive is within this range, a preferable phase separation structure can be obtained while reducing the additive remaining in the organic active layer. As described above, a bulk heterojunction active layer can be formed by applying a coating liquid (ink) containing a p-type semiconductor compound, an n-type semiconductor compound, and an additive.

[P-i-n stacked active layer]
The p-i-n stacked active layer includes a p-type semiconductor layer containing a p-type semiconductor compound, an i layer in which a p-type semiconductor compound and an n-type semiconductor compound are mixed, and n containing an n-type semiconductor compound. And a stacked type semiconductor layer. The p-i-n stacked active layer has an advantage that a portion where a photocurrent can be generated can be thickened. A p-i-n stacked active layer can be manufactured by forming a p-type semiconductor layer, an i-layer, and an n-type semiconductor layer, respectively. The formation method of a layer is not specifically limited, For example, the apply | coating method or a vapor deposition method can be used. The p-type semiconductor layer, i-layer, and n-type semiconductor layer may be formed by different methods.

  The p-type semiconductor layer and the n-type semiconductor layer constituting the p-i-n stacked active layer can be formed in the same manner as the above-described thin-film stacked active layer. Further, the i layer constituting the p-i-n stacked type active layer can be formed in the same manner as the above-described bulk heterojunction type active layer. Similarly to the method for forming the bulk heterojunction active layer, when the i layer is formed by a coating method, an additive may be further added to the coating solution containing the p-type semiconductor compound and the n-type semiconductor compound.

  The p-type semiconductor compound contained in the p-type semiconductor layer and the p-type semiconductor compound contained in the i layer may be the same or different. The n-type semiconductor compound contained in the n-type semiconductor layer and the n-type semiconductor compound contained in the i layer may be the same or different. That is, the p-i-n stacked active layer only needs to contain a dihydromethano group-added fullerene compound described later in at least one of the n-type semiconductor layer and the i layer. However, since the dihydromethano group-added fullerene compound described later has suitable properties as an n-type semiconductor compound, it is more preferable that both the n-type semiconductor layer and the i layer contain a dihydromethano group-added fullerene compound described later. .

  There is no restriction | limiting in the film thickness of i layer in a pin laminated structure. However, it is usually 5 nm or more, preferably 10 nm or more, and usually 500 nm or less, preferably 200 nm or less. The film thickness of the i layer is preferably 500 nm or less from the viewpoint of reducing the series resistance. It is preferable that the thickness of the n-type semiconductor layer is 10 nm or more because a region where carrier separation can occur in the photoelectric conversion element is large, and thus a current obtained can be large.

  Further, when the i layer has a nanostructure in the p-i-n stacked structure, a route for transporting electrons and holes generated from the mixed junction layer (i layer) can be formed, and the photocurrent can be increased. Particularly preferred. For example, the nanostructure refers to a state in which a p-type semiconductor compound and an n-type semiconductor compound are in contact with each other by forming irregularities with a depth of about 1 nm to 500 nm.

  In order to form the nanostructure, the following method can be performed. That is, a nanostructure is formed using a p-type semiconductor compound and a nanostructure-forming compound. Then, the nanostructure-forming compound and the n-type semiconductor compound are substituted. Thus, a nanostructure of the p-type semiconductor compound and the n-type semiconductor compound can be formed. As the nanostructure-forming compound, a compound having properties suitable for controlling the nanostructure such as high solubility in a solvent can be used. The use of an n-type semiconductor compound as the nanostructure-forming compound is suitable for forming a nanostructure. Specific examples of the nanostructure-forming compound include SIMEF2 (compound H10) described later.

  By using a nanostructure-forming compound for controlling the nanostructure, the nanostructure can be preferably controlled while using an n-type semiconductor compound suitable for a photoelectric conversion element such as a dihydromethano group-added fullerene compound described later. As a result, an increase in photocurrent and an improvement in open-circuit voltage can be achieved independently.

[Solvent of coating solution]
Examples of the solvent for the coating solution containing the p-type semiconductor compound, the coating solution containing the n-type semiconductor compound, and the coating solution containing the p-type semiconductor compound and the n-type semiconductor compound include p-type semiconductor compounds and / or n-type. Although it will not specifically limit if a semiconductor compound can be melt | dissolved uniformly, For example, aliphatic hydrocarbons, such as hexane, heptane, octane, isooctane, nonane, or decane; Toluene, xylene, mesitylene, cyclohexylbenzene, chlorobenzene, or orthodi Aromatic hydrocarbons such as chlorobenzene; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, tetralin or decalin; lower alcohols such as methanol, ethanol or propanol; acetone, methyl ethyl ketone Aliphatic ketones such as cyclohexane, cyclopentanone or cyclohexanone; aromatic ketones such as acetophenone or propiophenone; esters such as ethyl acetate, butyl acetate or methyl lactate; chloroform, methylene chloride, dichloroethane, trichloroethane, or trichloroethylene Halogen ethers of the above; ethers such as ethyl ether, tetrahydrofuran or dioxane; or amides such as dimethylformamide or dimethylacetamide.

  Among them, aromatic hydrocarbons such as toluene, xylene, mesitylene, cyclohexylbenzene, chlorobenzene or orthodichlorobenzene; cycloaliphatic carbonization such as cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, tetralin or decalin Hydrogens; ketones such as acetone, methyl ethyl ketone, cyclopentanone or cyclohexanone; halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane or trichloroethylene; or ethers such as ethyl ether, tetrahydrofuran or dioxane. More preferably, non-halogen aromatic hydrocarbons such as toluene, xylene, mesitylene or cyclohexylbenzene; non-halogen ketones such as cyclopentanone or cyclohexanone; aromatic ketones such as acetophenone or propiophenone; tetrahydrofuran, cyclohexane Alicyclic hydrocarbons such as pentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, tetralin or decalin; ketones such as acetone, methyl ethyl ketone, cyclopentanone or cyclohexanone; or non-halogens such as 1,4-dioxane Aliphatic ethers. Particularly preferred are non-halogen aromatic hydrocarbons such as toluene, xylene, mesitylene or cyclohexylbenzene.

  In addition, 1 type of solvent may be used independently as a solvent, and arbitrary 2 or more types of solvents may be used together by arbitrary ratios. When two or more solvents are used in combination, it is preferable to combine a low boiling point solvent having a boiling point of 60 to 150 ° C and a high boiling point solvent having a boiling point of 180 to 250 ° C. Examples of combinations of low boiling point solvents and high boiling point solvents include non-halogen aromatic hydrocarbons and alicyclic hydrocarbons, non-halogen aromatic hydrocarbons and aromatic ketones, ethers and alicyclic carbonization. Examples thereof include hydrogens, ethers and aromatic ketones, aliphatic ketones and alicyclic hydrocarbons, or aliphatic ketones and aromatic ketones. Specific examples of preferred combinations include toluene and tetralin, xylene and tetralin, toluene and acetophenone, xylene and acetophenone, tetrahydrofuran and tetralin, tetrahydrofuran and acetophenone, methyl ethyl ketone and tetralin, methyl ethyl ketone and acetophenone, and the like.

<1.1.1 n-type semiconductor compound>
The n-type semiconductor compound according to this embodiment includes a dihydromethano group-added fullerene compound according to the present application (hereinafter referred to as a methanofullerene compound). Hereinafter, the methanofullerene compound according to this embodiment will be described. The n-type semiconductor compound used in the present embodiment may be a single compound or a mixture of a plurality of compounds.

[(1) Methanofullerene compound according to this embodiment]
The methanofullerene compound according to this embodiment is represented by the following general formula (I).

In the above general formula (I), FLN represents fullerene, and the dihydromethano group (—C ¹ H ₂ —) is added to the same 5-membered ring or 6-membered ring in the fullerene skeleton. In particular, in the general formula (I), it is preferable that one dihydromethano group, that is, C ¹ is bonded to two adjacent carbon atoms in the fullerene skeleton. That is, the methanofullerene compound according to this embodiment is preferably a compound represented by the following general formula (Ia). Further, an additional group R is bonded to the fullerene. Details of the fullerene (FLN) and the addition group R will be described later.

  In the above general formula (I), m is 1 or 2. That is, the methanofullerene compound according to this embodiment has one or two dihydromethano groups. As the number of m increases, the LUMO level of the methanofullerene compound tends to increase. Therefore, m is preferably 1 in order not to increase the LUMO level too much.

  In said general formula (I), n is an integer of 0-10. From the viewpoint of increasing the LUMO level of the methanofullerene compound, n is preferably 1 or more. Further, n is preferably 4 or less and more preferably 2 from the viewpoint of suppressing steric hindrance of the methanofullerene compound and preventing the LUMO level from becoming too high.

  The relative configuration of the additional group R and the dihydromethano group is not particularly limited. Moreover, when there are a plurality of additional groups R, the relative arrangement between the additional groups R is not particularly limited. Even when there are a plurality of dihydromethano groups, the relative arrangement between the dihydromethano groups is not particularly limited.

[(1-1) Fullerene according to this embodiment (FLN)]
The fullerene (FLN) according to the present embodiment 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. The fullerene, for _{example, C 60, C 70, C} 76, C 78, C 82, C 84, C 90, C 94, C 96 and the like. Furthermore, the fullerene according to the present embodiment may be a higher-order carbon cluster having more carbon than these. Among these, _C60 and _C70 are preferable. C ₆₀ and more preferably at a point that may indicate the point and a suitable electron-accepting availability, C ₇₀ is also preferable in that can exhibit suitable electron-accepting.

A mixture of fullerenes having different carbon numbers may be used. In the case of using mixed and, it is preferable to use a mixture of C ₆₀ and C _70. When a mixture of C ₆₀ and C ₇₀ is used, a small amount of fullerene having a larger number of carbon atoms may be mixed, and the mixed amount with respect to the entire fullerene is preferably 20% or less, more preferably 10%. %, 5%, 2%, 1%, 0.5%.

  Fullerenes in which part of the carbon-carbon bond on the fullerene ring is broken are also well known. The fullerene according to the present embodiment includes such a fullerene in which a part of the carbon-carbon bond on the fullerene ring is broken. In addition, fullerenes in which some carbon atoms constituting the fullerene are replaced with other atoms, and fullerenes including a metal atom, a nonmetallic atom, or an atomic group composed of these atoms are also well known. The fullerene according to the present embodiment includes these fullerenes.

[(1-2) Additional group R according to this embodiment]
In the general formula (I), the additional group R (substituent, organic group) added to fullerene (FLN) is arbitrary. For example, as the additional group R, a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an amino group, an ester group, a carboxyl group, a carbonyl group, an oxycarbonyl group, an acetyl group, a sulfonyl group, a silyl group, a boryl group, a nitrile group, an alkyl group Group, perfluoroalkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, aromatic hydrocarbon group and aromatic heterocyclic group.

The additional group R may be a monovalent substituent or a divalent or higher valent substituent. For example, when the additional group R is a divalent substituent, the additional group R may be bonded to the fullerene in any way. For example, as in the following formula, one additional group R may be bonded to two adjacent carbon atoms on the fullerene ring. Further, one additional group R may be bonded to two carbon atoms located on the fullerene ring with one carbon atom interposed therebetween. Furthermore, one additional group R may be bonded to two carbon atoms located between two or more carbon atoms on the fullerene ring. One additional group R is preferably bonded to the same 5-membered ring or 6-membered ring in the fullerene skeleton.

  As the alkyl group, those having 1 to 20 carbon atoms are preferable, for example, methyl group, ethyl group, i-propyl group, n-propyl group, n-butyl group, t-butyl group, n-hexyl group and cyclohexyl group. Etc.

  As a perfluoroalkyl group, a C1-C12 thing is preferable, for example, a trifluoromethyl 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 an alkoxy group, a C1-C20 thing is preferable, for example, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, ethylhexyloxy group, benzyloxy group And a linear or branched alkoxy group such as t-butoxy group.

  As a carbonyl group, a C2-C16 thing is preferable, for example, an acetyl group, a phenylcarbonyl group, etc. are mentioned.

  As an oxycarbonyl group, a C1-C10 thing is preferable, for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc. are mentioned.

  As the aryloxy group, those having 2 to 20 carbon atoms are preferable, and examples thereof include a phenoxy group.

  As an alkylthio group, a C1-C20 thing is preferable, for example, a methylthio group, an ethylthio group, etc. are mentioned.

  As an arylthio group, a C2-C20 thing is preferable, for example, a phenylthio group etc. are mentioned.

  Examples of amino groups include unsubstituted amino groups; alkylamino groups such as dimethylamino groups, diethylamino groups, and diisopropylamino groups; and arylamino groups such as diphenylamino groups, ditolylamino groups, carbazolyl groups, and phenylcarbazolyl groups. Is mentioned.

  As the silyl group, an unsubstituted or substituted silyl group can be used. Examples thereof include silyl groups having an alkyl group or an aryl group as a substituent, such as a trimethylsilyl group, a dimethylphenyl group, and a triphenylsilyl group.

  As the boryl group, an unsubstituted or substituted boryl group can be used. Examples thereof include a dimesitylboryl group substituted with an aryl group.

  As the aromatic group, an aromatic hydrocarbon group and an aromatic heterocyclic group can be used.

  As an aromatic hydrocarbon group, a C6-C20 thing is preferable, These are not limited to a monocyclic group at all, A condensed polycyclic hydrocarbon group and a ring condensed hydrocarbon group may be sufficient. For example, phenyl group, naphthyl group, phenanthryl group, biphenyl group, biphenylenyl group, anthryl group, pyrenyl group, fluorenyl group, azulenyl group, acenaphthenyl group, fluoranthenyl group, naphthacenyl group, perylenyl group, pentacenyl group, triphenylenyl group and quarter A phenyl group etc. are mentioned. Among these, a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a pyrenyl group, a fluorenyl group, an acenaphthenyl group, a fluoranthenyl group, a perylenyl group, and a triphenylenyl group are preferable.

  As an aromatic heterocyclic group, a C2-C20 thing is 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 group, phenoxathienyl group, xanthenyl group, benzofuranyl group, thiantenyl group, indolizinyl group, phenoxazinyl group, phenothiazinyl group, acridinyl group, phenanthridinyl group, phenanthrolinyl group, quinolyl group, isoquinolyl group And indolyl group and quinoxalinyl group. Among these, 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 , Phenylcarbazolyl group, xanthenyl group and phenoxazinyl group are preferable.

  The additional group R exemplified so far may further have a substituent. The substituent that may be present is not particularly limited, and may have the group described above as an example of the additional group R. The substituent is preferably a halogen atom, hydroxyl group, cyano group, amino group, carboxyl group, ester group, carbonyl group, oxycarbonyl group, acetyl group, sulfonyl group, silyl group, boryl group, nitrile group, alkyl group, alkenyl group. Alkynyl group, alkoxy group, aryl group, aryloxy group, arylamino group, arylthio group, alkylthio group, perfluoroalkyl group, aromatic hydrocarbon group and aromatic heterocyclic group. These may be connected with adjacent substituents to form a ring. The substituent that the additional group R has may further have a substituent. The further substituent is not particularly limited, and may have the group described above as an example of the additional group R.

  When the additional group or the substituent further included in the additional group has the ability to coordinate to the metal, a metal complex may be formed through a coordinate bond with the metal atom.

The methanofullerene compound according to the present embodiment has a structure represented by at least one of the following general formulas (II) and (III) in addition to the methanofullerene structure (methano group (—CH ₂ — bonded to fullerene)). It is preferable to have.

In the formulas (II) and (III), FLN represents the fullerene according to the present embodiment. In the formula, p and q are each an integer, and the sum of p and q is usually 1 to 5. From the viewpoint of suppressing the steric hindrance and preventing the LUMO level of the methanofullerene compound from becoming too high, the total of p and q is preferably 2 or less, more preferably 1. R ^′ , R ^″ , R ^{′ ″} each independently represents an additional group that is added to the fullerene skeleton, and corresponds to the above-described additional group R. (II) and (III) each additional group R in ^{', R'',R'} '' are preferably attached to the same five-membered ring or six-membered ring in the fullerene skeleton.

In the formula (II), R ^′ and R ^″ may form a ring directly or through another substituent. In this case, the following equation, and the carbon on the fullerene ^{ring 'carbon} and R on the fullerene rings are ^attached' R ^'are bonded, may be bonded to each other. Further, the carbon on the fullerene ring to which R ^′ is bonded and the carbon on the fullerene ring to which R ^″ is bonded may be bonded via one carbon atom. Furthermore, the carbon on the fullerene ring to which R ^′ is bonded and the carbon on the fullerene ring to which R ^″ is bonded may be bonded via two or more carbon atoms.

In formula (III), R ^{′ ″} is a divalent addition group, and the bond to carbon on the fullerene is as described above.

Among the partial structures represented by the formula (II), in particular, the partial structure represented by the following general formula (n1), (n2), (n3), (n5), (n6) or (n7) The methanofullerene compound according to the embodiment preferably has. Moreover, among the partial structures represented by the formula (III), the methanofullerene compound according to this embodiment preferably has a partial structure represented by the following general formula (n4). The methanofullerene compound according to this embodiment may have one or more of partial structures (organic groups) represented by the following formulas (n1) to (n7).

  In formulas (n1) to (n7), FLN represents a fullerene to which a dihydromethano group is added according to this embodiment. R, s, t, u, v, w, and x are independent integers. The methanofullerene compound according to the present embodiment can have one or more of the partial structures represented by the formulas (n1) to (n7). In this case, generally, the sum of r, s, t, u, v, w, and x is an integer of 1 to 5. From the viewpoint of suppressing the steric hindrance of the methanofullerene compound and preventing the LUMO level from becoming too high, the total of r, s, t, u, v, w, and x is preferably 2 or less, and more preferably 1.

In the formulas (n1) to (n7), the substituents R ^{1 to} R ¹⁷ may be arbitrary substituents, and various substituents described as examples of the additional group R according to this embodiment can be used. The substituents Ar ^{1 to} Ar ⁵ may be any aromatic group, and various aromatic groups described as examples of the additional group R according to this embodiment can be used. Hereinafter, examples of particularly preferable substituents will be described.

In general formula (n1), L is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less, and particularly preferably 1. R ¹ 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 isobutyl group is more preferable, and a methyl group and an ethyl group are especially preferable.

  As an alkoxy group, a C1-C10 alkoxy group is preferable, a C1-C8 alkoxy group is more preferable, a C1-C6 alkoxy group is still more preferable, and a methoxy group and an ethoxy group are especially preferable.

  As the aromatic group, an aromatic hydrocarbon group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 2 to 20 carbon atoms are preferable, and a phenyl group, a thienyl group, a furyl group, and a pyridyl group are more preferable. More preferred are groups and thienyl groups.

  The substituent which may be substituted on the alkyl group is a halogen atom or a silyl group. The halogen atom that may be substituted is preferably a fluorine atom.

  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 ^{2 to} R ⁴ in the general formula (n1) each represent an independent substituent, and a hydrogen atom, an alkyl group having 1 to 14 carbon atoms which may have a substituent, or an optionally substituted carbon. It is an aromatic group which may have a fluorinated alkyl group of formulas 1 to 14 and a substituent.

  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, and n-hexyl group are preferable.

  As the fluorinated alkyl group, a perfluorooctyl group, a perfluorohexyl group, and a perfluorobutyl group are preferable.

  The aromatic group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 2 to 20 carbon atoms, more preferably a phenyl group, a thienyl group, a furyl group and a pyridyl group, and a phenyl group and a thienyl group. More preferred are groups.

  The substituent that the aromatic group may have is 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, and 3 to 3 carbon atoms. 10 aromatic groups are preferable, a fluorine atom and an alkoxy group having 1 to 14 carbon atoms are more preferable, and a methoxy group, an n-butoxy group, and a 2-ethylhexyloxy group are further preferable.

  When an aromatic group has a substituent, although there is no limitation in the number, 1-3 are preferable and 1 is more preferable. When the aromatic group has a plurality of substituents, the types of the substituents may be different, but are preferably the same.

R ^{5 to} R ⁹ 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. is there.

  As the alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group and an octyl group are preferable, and a methyl group is more preferable.

  The aromatic group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 2 to 20 carbon atoms, more preferably a phenyl group and a pyridyl group, and further preferably a phenyl group.

  Although there is no limitation in particular as a substituent which an aromatic group may have, a fluorine atom, a C1-C14 alkyl group, a C1-C14 fluorinated alkyl group, and a C1-C14 alkoxy group are preferable. And more preferably an alkoxy group having 1 to 14 carbon atoms, and even more preferably a methoxy group.

  When it has a substituent, the number is not limited, but 1 to 3 is preferable, and 1 is more preferable. 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, and includes a phenyl group and a naphthyl group. Group, phenanthryl group, anthryl group, fluorenyl group, pyrenyl group, perylenyl group, biphenyl group, terphenyl group, thienyl group, furyl group, pyridyl group, pyrimidinyl group, quinolyl group, quinoxalyl group, pyrazinyl group, imidazolyl group, pyrazolyl group , Oxazolyl group, thiazolyl group, oxadiazolyl group, pyrrolyl group, triazolyl group, thiadiazolyl group, benzothienyl group, benzofuryl group, furfuryl group, dibenzothienyl group, thienothienyl group, dibenzofuryl group, phenanthryl group, carbazolyl group, benzoquinoxari Nyl and phenylcarbazolyl groups are preferred More preferred are phenyl, thienyl, furyl, thiazolyl, pyrrolyl, triazolyl and thiadiazolyl groups.

  Although there is no limitation as a substituent which you may have, a fluorine atom, a chlorine atom, a hydroxyl group, a cyano group, a silyl group, a boryl group, an amino group which may be substituted with an alkyl group, 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, an alkylcarbonyl group having 1 to 14 carbon atoms, an alkylthio group having 1 to 14 carbon atoms, an alkenyl group having 1 to 14 carbon atoms, carbon Preferred are 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, and a heterocyclic group having 2 to 20 carbon atoms. 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, and an arylcarbonyl group are more preferable.

  As the alkyl group having 1 to 14 carbon atoms, a methyl group, an ethyl group, and a propyl group are preferable. As a C1-C14 alkoxy group, a methoxy group, an ethoxy group, and a propoxyl group are preferable. As the alkylcarbonyl group having 1 to 14 carbon atoms, an acetyl group is preferable.

  As the ester group, a methyl ester group and an n-butyl ester group are 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 ^{10 to} R ¹³ in the general formula (n3) may each independently have a hydrogen atom, an alkyl group that may have a substituent, an amino group that may have a substituent, or a substituent. It is a good alkoxy group or an optionally substituted alkylthio group. R ¹⁰ or R ¹¹ may form a ring with either R ¹² or R ¹³ .

The structure in the case of forming a ring can be represented by, for example, the following general formula (n8), which is a bicyclo structure in which an aromatic group is condensed.

The y in the general formula (n8) in the same as defined above t, Ar ¹ is the same as Ar ¹ as defined above. X is an oxygen atom, a sulfur atom, an amino group, an alkylene group or an arylene group. The alkylene group is preferably an alkylene group having 1 or 2 carbon atoms. As the arylene group, those having 5 to 12 carbon atoms are preferable, and examples thereof include 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.

The structure represented by the general formula (n3) is particularly preferably a structure represented by the following general formula (n9) or general formula (n10). However, although in the formula (n3) was assumed that there is an aromatic ring Ar ^1, it may be present aliphatic ring instead of Ar ^1, a hydrogen atom in place of Ar ^1, alkyl group, a halogen atom As an example of the additional group R, other substituents as described above may be bonded.

One of R ¹⁴ and R ¹⁵ in the general formula (n4) may have a hydrogen atom, an alkoxycarbonyl group, an alkyl group having 1 to 14 carbon atoms which may have a substituent, or a substituent. The other is a good aromatic group, and the other is an alkoxycarbonyl group, an alkyl group having 1 to 14 carbon atoms which may have a substituent, or an aromatic group which may have a substituent.

  The alkoxy group in the alkoxycarbonyl group is preferably an alkoxy group having 1 to 12 carbon atoms and a fluorinated alkoxy group, more preferably an alkoxy group having 1 to 12 carbon atoms, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group. N-butoxy group, isobutoxy group, n-hexoxy group, octoxy group, 2-propylpentoxy group, 2-ethylhexoxy group, 2-ethylhexoxy group, cyclohexylmethoxy group and benzyloxy group are more preferable, methoxy group, ethoxy group , Isopropoxy group, n-butoxy group, isobutoxy group and n-hexoxy group are 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. There is no particular limitation on the substituent that the alkyl group may have, but an alkoxycarbonyl group is preferred. The alkoxy group of the alkoxycarbonyl group is preferably an alkoxy group having 1 to 14 carbon atoms and a fluorinated alkoxy group, more preferably an alkoxy group having 1 to 14 carbon atoms, and a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group. Group, n-butoxy group, isobutoxy group, n-hexoxy group, octoxy group, 2-propylpentoxy group, 2-ethylhexoxy group, cyclohexylmethoxy group and benzyloxy group are more preferable, and methoxy group and n-butoxy group are particularly preferable. preferable.

  As the aromatic group, an aromatic hydrocarbon group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 2 to 20 carbon atoms are preferable, and a phenyl group, a biphenyl group, a thienyl group, a furyl group, and a pyridyl group are preferable. More preferred are groups and thienyl groups. 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 and 2-ethylhexyloxy group are particularly preferable. 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 or the same, preferably the same.

As the structure of the general formula (n4), a structure in which R ¹⁴ and R ¹⁵ are both alkoxycarbonyl groups, a structure in which R ¹⁴ and R ¹⁵ are both aromatic groups, and one of R ¹⁴ and R ¹⁵ is aromatic A structure in which the other group is an alkyl group which may have a substituent is preferable. In particular, a structure in which R ¹⁴ is an aromatic group and R ¹⁵ is a 3- (alkoxycarbonyl) propyl group is preferable.

In general formulas (n5) and (n6), Ar ^{2 to} Ar ⁵ each independently have an aromatic hydrocarbon group having 6 to 20 carbon atoms or a substituent which may have a substituent. Or an aromatic heterocyclic group having 2 to 20 carbon atoms.

  The aromatic hydrocarbon group is not particularly limited as long as it is an aromatic hydrocarbon group having 6 to 20 carbon atoms, but it is a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, a polycyclic hydrocarbon group. Etc. Specifically, monocyclic hydrocarbon groups such as phenyl groups, phenanthryl groups, naphthyl groups, anthryl groups, fluorenyl groups, pyrenyl groups, perylenyl groups and other condensed polycyclic hydrocarbon groups, biphenyl groups, terphenyls, etc. Examples include polycyclic hydrocarbon groups. Among them, a monocyclic hydrocarbon group such as a phenyl group is preferable, and a condensed polycyclic hydrocarbon group such as a naphthyl group or an anthryl group is preferable. More preferred are a phenyl group and a naphthyl group.

  The aromatic heterocyclic group is not particularly limited as long as it is an aromatic heterocyclic group having 2 to 20 carbon atoms, and examples thereof include a monocyclic heterocyclic group and a condensed polycyclic aromatic heterocyclic group. Specifically, monocyclic heterocyclic rings such as pyridyl group, pyrazinyl group, pyrimidinyl group, imidazolyl group, pyrazolyl group, thienyl group, furyl group, oxazolyl group, thiazolyl group, oxadiazolyl group, pyrrolyl group, triazolyl group, thiadiazolyl group, etc. Group, benzothienyl group, benzofuryl group, furfuryl group, dibenzothienyl group, thienothienyl group, dibenzofuryl group, phenanthryl group, carbazolyl group, quinoxalinyl group, benzoquinoxalinyl group, phenylcarbazolyl group, etc. An aromatic heterocyclic group is mentioned. Among them, pyrazinyl group, thienyl group, furyl group, thiazolyl group, pyrrolyl group, triazolyl group, thiadiazolyl group are preferable among monocyclic heterocyclic groups, benzofuryl group, furfuryl group, benzothienyl group, thienothienyl group, quinoxalinyl group A benzoquinoxalinyl group is preferred among the condensed polycyclic aromatic heterocyclic groups.

The upper limit of the number of substituents is not particularly limited, but is preferably 5 or less, more preferably 3 or less, for each of Ar ^{2 to} Ar ³ . When there are a plurality of substituents, the type may be the same or different.

  Specific examples of the substituent that the aromatic hydrocarbon group or the aromatic heterocyclic group may have include a halogen atom, an oxygen atom, a sulfur atom, a hydroxyl group, a cyano group, an amino group, an ester group, and a carboxyl group. , Carbonyl group, acetyl group, sulfonyl group, silyl group, boryl group, cyano group, nitro group, fluorinated alkyl group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, aromatic Family groups and the like.

  As the alkyl group, those having 1 to 20 carbon atoms are preferred, and specific examples include methyl group, ethyl group, i-propyl group, n-propyl group, n-butyl group, t-butyl group, n-hexyl group, A cyclohexyl group etc. are mentioned.

  The alkenyl group preferably has 2 to 20 carbon atoms, and specific 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 specific examples include a methylethynyl group, a phenylethynyl group, a trimethylsilylethynyl group, and the like.

  As the alkoxy group, those having 1 to 20 carbon atoms are preferable, and specific examples include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group and the like. A linear or branched alkoxy group is mentioned.

  The aryloxy group preferably has 6 to 20 carbon atoms, and specific examples include a phenoxy group.

  As an alkylthio group, a C1-C20 thing is preferable and a methylthio group, an ethylthio group, etc. are mentioned as a specific example.

  As the arylthio group, those having 6 to 20 carbon atoms are preferable, and specific examples thereof include a phenylthio group.

  Examples of the amino group include alkylamino groups such as methylamino group, ethylamino group, dimethylamino group, diethylamino group and diisopropylamino group, and arylamino groups such as diphenylamino group, ditolylamino group and carbazoyl group.

  Specific examples of the silyl group include a silyl group having an alkyl group or an aryl group as a substituent such as a trimethylsilyl group, a dimethylphenyl group, or a triphenylsilyl group.

  Examples of the boryl group include a dimesitylboryl group substituted with an aryl group.

  As the aromatic group, phenyl group, naphthyl group, phenanthryl group, biphenylenyl group, triphenylenyl group, anthryl group, pyrenyl group, fluorenyl group, azulenyl group, acenaphthenyl group, fluoranthenyl group, naphthacenyl group, perylenyl group, pentacenyl group, Aromatic hydrocarbon group such as quarterphenyl group, 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, benzofuryl group, thiantenyl group, indolizinyl group, phenoxazinyl group, phenothiazinyl group, Jiniru group, phenanthridinyl group, quinolyl group, isoquinolyl group, indolyl group, an aromatic heterocyclic group such as a quinoxalinyl group. Preferably, an aromatic hydrocarbon group such as phenyl group, naphthyl group, phenanthryl group, triphenylenyl group, anthryl group, pyrenyl group, fluorenyl group, acenaphthenyl group, fluoranthenyl group, perylenyl group, triphenylenyl group; pyridyl group, pyrazinyl group , Pyrimidinyl group, pyrazolyl group, quinolyl group, isoquinolyl group, imidazolyl group, acridinyl group, phenanthridinyl group, quinoxalinyl group, dibenzofuryl group, dibenzothienyl group, phenylcarbazolyl, xanthenyl group, phenoxazinyl group, etc. It is a heterocyclic group.

  More preferable types of these substituents are halogen atoms, alkyl groups having 1 to 14 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, and alkyl fluorides having 1 to 12 carbon atoms. Groups, alkoxy groups, ester groups, alkylcarbonyl groups, arylcarbonyl groups, amino groups, amide groups, cyano groups, carboxyl groups, and aromatic groups.

  The above substituent may further have a substituent. Further, the substituents that may be present include alkyl groups, aryl groups, arylamino groups, alkyl groups, fluorinated alkyl groups, halide groups, carboxyl groups, cyano groups, alkoxyl groups, aryloxy groups, carbonyl groups, oxy groups. Examples include a carbonyl group, a carboxylic acid group, and a heterocyclic group. Preferably, an aryl group having 6 to 16 carbon atoms, an arylamino group having 12 to 30 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a perfluoroalkyl group having 1 to 12 carbon atoms, a fluoro group, and 1 to 10 carbon atoms. An alkoxycarbonyl group, a cyano group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 16 carbon atoms, a carbonyl group having 2 to 16 carbon atoms, and an aromatic heterocyclic group having 2 to 20 carbon atoms.

In General Formula (n7), R ^{16 to} R ¹⁷ each independently have a hydrogen atom, an alkoxycarbonyl group, an optionally substituted alkyl group having 1 to 14 carbon atoms, or a substituent. May be an aromatic group.

  The alkoxy group in the alkoxycarbonyl group is preferably an alkoxy group having 1 to 12 carbon atoms and a fluorinated alkoxy group, more preferably an alkoxy group having 1 to 12 carbon atoms, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group. N-butoxy group, isobutoxy group, n-hexoxy group, octoxy group, 2-propylpentoxy group, 2-ethylhexoxy group, 2-ethylhexoxy group, cyclohexylmethoxy group and benzyloxy group are more preferable, methoxy group, ethoxy group , Isopropoxy group, n-butoxy group, isobutoxy group and n-hexoxy group are 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. There is no particular limitation on the substituent that the alkyl group may have, but an alkoxycarbonyl group is preferred. The alkoxy group of the alkoxycarbonyl group is preferably an alkoxy group having 1 to 14 carbon atoms and a fluorinated alkoxy group, more preferably an alkoxy group having 1 to 14 carbon atoms, and a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group. Group, n-butoxy group, isobutoxy group, n-hexoxy group, octoxy group, 2-propylpentoxy group, 2-ethylhexoxy group, cyclohexylmethoxy group and benzyloxy group are more preferable, n-butoxy group and n-hexoxy group Is particularly preferred.

  The aromatic group is an 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 biphenyl group, a thienyl group, a furyl group, or a pyridyl group. More preferred is a phenyl group. 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, and more preferably It is a C1-C14 alkoxy group, More preferably, they are a methoxy group and 2-ethylhexyloxy 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 or the same, preferably the same.

  Specific examples of the methanofullerene compound according to this embodiment include the following. In the following formulae, Me, Et, n-Bu, and Ph represent a methyl group, an ethyl group, an n-butyl group, and a phenyl group, respectively.

In the above, e is 1 or 2, f is 1 or 2, g is an integer of 1 to 4, and h is an integer of 1 to 5. In the above has been illustrated with respect to the case of using the C ₆₀ as fullerene (FLN) according to the present embodiment, C ₆₀ can be replaced with a different fullerene number of carbon atoms, such as C _70.

  The methanofullerene compound according to the present embodiment is not particularly limited, but has high stability and tends to be difficult to remove an additional group by heating. The temperature at which the compound decomposes is usually 180 ° C. or higher, preferably 200 ° C. or higher. The decomposition temperature may be measured by a known method, and examples thereof include thermogravimetry (TGA) and differential thermal-thermogravimetric simultaneous measurement (TG-DTA).

  Although there is no limitation in particular as a glass transition temperature of the methanofullerene compound which concerns on this embodiment, 50 degreeC or more is preferable, More preferably, it is 70 degreeC or more. The upper limit is not particularly limited and is usually 350 ° C. or lower, preferably 400 ° C. or lower, but the glass transition temperature may not be observed. When the glass transition temperature is 50 ° C. or higher, the amorphous film of the compound is kept stable, and the functional stability as an n-type semiconductor is maintained, so that the efficiency of the photoelectric conversion element is maintained or improved. Moreover, durability when used as a solar cell is also increased. Also. What is necessary is just to measure a glass transition temperature by a well-known method, for example, differential thermal-thermogravimetric simultaneous measurement (TG-DTA) and differential scanning calorimetry (DSC) are mentioned.

  It is preferable that both the decomposition temperature and the glass transition temperature of the methanofullerene compound according to the present embodiment are high, because the temperature range that can be heated at the time of device preparation is widened and the durability when used as a solar cell is also increased. . The decomposition temperature is preferably 180 ° C. or higher and the glass transition temperature is 50 ° C. or higher, more preferably the decomposition temperature is 200 ° C. or higher and the glass transition temperature is 70 ° C. or higher.

  The value of the lowest unoccupied molecular orbital (LUMO) of the methanofullerene compound according to the present embodiment is not particularly limited, and the value varies depending on the structure and number of additional groups. For example, the vacuum level calculated by a cyclic voltammogram measurement method is used. The value for the position is usually −3.95 eV or higher, preferably −3.85 eV or higher, more preferably −3.80 eV or higher, and particularly preferably −3.75 eV or higher. On the other hand, it is usually −3.30 eV or less, preferably −3.40 eV or less, more preferably −3.50 eV or less.

  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. If the LUMO of the electron acceptor is too high, the electron transfer is difficult to occur, so that the short circuit current (Jsc) tends to be low. 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, if the LUMO of the electron acceptor layer is too low, the Voc is low. Tend to be. The fullerene compound according to this embodiment has various LUMO levels depending on the structure and number of the additional groups, and an optimum derivative can be selected according to the type of electron donor to be combined.

  As a method for calculating the LUMO value of the methanofullerene compound according to the present embodiment, there are a theoretically calculated method and a method of actually measuring. The theoretically calculated values include semi-empirical molecular orbital methods and non-empirical molecular orbital methods, and the actual measurement methods include ultraviolet-visible absorption spectrum measurement method or cyclic voltammogram measurement method. can give. In this specification, LUMO is measured using a cyclic voltammogram measurement method.

  Adding a dihydromethano group to the fullerene compound has an effect of increasing the LUMO of the fullerene compound while suppressing an increase in steric hindrance of the fullerene compound. By suppressing the steric hindrance, the interaction between adjacent fullerene compounds or between the donor molecule and the fullerene compound is weakened, and the three-dimensional structure of the fullerene compound, such as a decrease in the efficiency of carrier transfer between fullerenes and electron transfer from the donor molecule, etc. It is considered that the negative effect due to the increase in disability can be suppressed. As described above, the open-circuit voltage (Voc) can be improved without greatly impairing the characteristics of the fullerene compound as an n-type semiconductor compound, and as a result, a highly efficient photoelectric conversion element can be obtained.

式（ｎ１１）および（ｎ１２）において、ＦＬＮはフラーレンを表し、ジヒドロメタノ基はフラーレン骨格中の同一の五員環もしくは六員環に付加されている。一般式（Ｉ）と同様に、ジヒドロメタノ基（−ＣＨ_２−）は、フラーレン骨格中の同一の五員環若しくは六員環に結合していることが好ましい。１つのジヒドロメタノ基は、フラーレン骨格中の隣接する２つの炭素原子に結合していることが特に好ましい。ｔ’，ｕ’は、上述のｔ，ｕと同様である。Ａｒ^１’も、上述のＡｒ^１と同様である。また、Ｒ^１０’〜Ｒ^１５’はそれぞれ、上述のＲ^１０〜Ｒ^１５と同様である。 [(1-3) Particularly preferred methanofullerene compound according to this embodiment]
The methanofullerene compound according to this embodiment is particularly preferably a fullerene compound represented by the following general formula (n11) or (n12).

In the formulas (n11) and (n12), FLN represents fullerene, and the dihydromethano group is added to the same 5-membered ring or 6-membered ring in the fullerene skeleton. As in the general formula (I), the dihydromethano group (—CH ₂ —) is preferably bonded to the same 5-membered ring or 6-membered ring in the fullerene skeleton. It is particularly preferable that one dihydromethano group is bonded to two adjacent carbon atoms in the fullerene skeleton. t ′ and u ′ are the same as t and u described above. Ar ^{1 ′} is the same as Ar ¹ described above. R ^{10 ′ to} R ^{15 ′} are the same as R ^{10 to} R ¹⁵ described above, respectively.

  These methanofullerene compounds are excellent in semiconductor characteristics because the distance between the fullerene molecules can be reduced because the steric hindrance of the dihydromethano group is small. Therefore, it can be used not only for the active layer of a photoelectric conversion element but also for various electronic devices. Examples of the electronic device include an element that controls current and voltage by applying voltage, an element that controls voltage and current by applying a magnetic field, and an element that controls voltage and current by applying a chemical substance. Examples of this control include rectification, switching, amplification, and oscillation. The corresponding devices currently implemented in silicon and the like include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements, chemical sensors, etc., or combinations of these elements. Examples include integrated devices. In addition, since it has high solubility in a solvent and excellent film-forming properties, it is suitable for use in a device using a coating or printing process.

[(2) Method for producing methanofullerene compound according to this embodiment]
In the present embodiment, although there is no particular limitation, the dihydromethano group added to fullerene is a compound (B) having a hydrogen atom and a silylmethyl group at the same time, or a silylmethyl group-added dimer compound ( C, fullerene dimer) can be reacted with an oxidizing agent.

[(2-1) Structure of Compound B]
In the general formula (B), the hydrogen atom and the silylmethyl group are bonded to the same five-membered or six-membered ring on the fullerene ring. The hydrogen atom and the silylmethyl group are usually bonded on the same six-membered ring, preferably in the 1,2-position or 1,4-position positional relationship, more preferably in the 1,2-position. It is in a positional relationship. Fln in the general formula (B) represents a fullerene to which an organic group may be added, and the organic group has the same meaning as the additional group R in the above general formula (I).

R < ²¹ > -R < ²³ > in general formula (B) represents an independent substituent, respectively, and has a hydrogen atom, the C1-C30 hydrocarbon group which may have a substituent, and a substituent. May have an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms which may have a substituent, an amino group which may have a substituent, or a substituent. A good silyl group, an alkylthio group which may have a substituent (-SY ¹ , wherein Y ¹ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent), a substituent; An arylthio group (—SY ² , wherein Y ² represents an aryl group having 6 to 18 carbon atoms which may have a substituent), or may have a substituent good alkylsulfonyl group _(-SO 2 ^{Y 3,} wherein, ^{Y 3} good C 1-2 which may have a substituent It shows the alkyl group.), Which may have a substituent arylsulfonyl group (-SO 2 _Y ^4, wherein, Y ⁴ is an aryl group having 6 to 18 carbon atoms which may have a substituent Is shown.)

  Among these, Preferably, it has a C1-C30 hydrocarbon group which may have a substituent, a C1-C30 alkoxy group which may have a substituent, and a substituent. An aryloxy group having 6 to 30 carbon atoms which may be present, more preferably a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent. 1 to 30 alkoxy groups.

  The hydrocarbon group having 1 to 30 carbon atoms may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. When the hydrocarbon group having 1 to 30 carbon atoms is acyclic, it may be linear or branched. The hydrocarbon group having 1 to 30 carbon atoms includes an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkyldienyl group having 4 to 30 carbon atoms, Aryl group having 6 to 28 carbon atoms, alkylaryl group having 7 to 30 carbon atoms, arylalkyl group having 7 to 30 carbon atoms, cycloalkyl group having 4 to 30 carbon atoms, cycloalkenyl group having 4 to 30 carbon atoms, carbon C1-C15 alkyl group etc. which the C3-C15 cycloalkyl substituted are contained.

  The alkyl group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, dodecanyl and the like.

  The alkenyl group having 2 to 30 carbon atoms is preferably an alkenyl group having 2 to 20 carbon atoms, and more preferably an alkenyl group having 2 to 10 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, 2-methyl-1-propenyl groups, 2-methylallyl groups, 2-butenyl groups, and the like. it can.

  The alkynyl group having 2 to 30 carbon atoms is preferably an alkynyl group having 2 to 20 carbon atoms, and more preferably an alkynyl group having 2 to 10 carbon atoms. Examples of alkynyl groups include, but are not limited to, ethynyl groups, propynyl groups, butynyl groups, and the like.

  The alkyldienyl group having 4 to 30 carbon atoms is preferably an alkyldienyl group having 4 to 20 carbon atoms, and more preferably an alkyldienyl group having 4 to 10 carbon atoms. Examples of alkyldienyl groups include, but are not limited to, 1,3-butadienyl and the like.

  The aryl group having 6 to 28 carbon atoms is preferably an aryl group having 6 to 15 carbon atoms. Examples of aryl groups include, but are not limited to, phenyl groups, 1-naphthyl groups, 2-naphthyl groups, indenyl groups, biphenylyl groups, anthryl groups, phenanthryl groups, and the like.

  The alkylaryl group having 7 to 30 carbon atoms is preferably an alkylaryl group having 7 to 15 carbon atoms. Examples of alkylaryl groups include, but are not limited to, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group. , O-cumenyl group, m-cumenyl group, p-cumenyl group, mesityl group and the like.

  The arylalkyl group having 7 to 30 carbon atoms is preferably an arylalkyl group having 7 to 12 carbon atoms. Examples of alkylaryl groups include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, A 3-phenylpropyl group, a 4-phenylbutyl group, a 5-phenylpentyl group, and the like can be given.

  The cycloalkyl group having 4 to 30 carbon atoms is preferably a cycloalkyl group having 4 to 10 carbon atoms. Examples of the cycloalkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and the like.

  The cycloalkenyl group having 4 to 30 carbon atoms is preferably a cycloalkenyl group having 4 to 10 carbon atoms. Examples of the cycloalkenyl group include, but are not limited to, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and the like.

  The alkoxy group having 1 to 30 carbon atoms is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 6 carbon atoms. Examples of alkoxy groups include, but are not limited to, methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, pentyloxy, and the like.

  The aryloxy group having 6 to 30 carbon atoms is preferably an aryloxy group having 6 to 10 carbon atoms. Examples of aryloxy groups include, but are not limited to, phenyloxy groups, naphthyloxy groups, biphenyloxy groups, and the like.

An alkylthio group (—SY ¹ , wherein Y ¹ represents an optionally substituted alkyl group having 1 to 20 carbon atoms) and an alkylsulfonyl group (—SO ₂ Y ³ , wherein Y ³ Represents an optionally substituted alkyl group having 1 to 20 carbon atoms.), Y ¹ and Y ³ are preferably alkyl groups having 1 to 10 carbon atoms, and 1 to 6 carbon atoms. More preferably, it is an alkyl group. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, dodecanyl. Groups and the like.

An arylthio group (-SY ^2, wherein, ^{Y 2} is shown which may have a substituent aryl group having 6 to 18 carbon atoms.) And an arylsulfonyl group _(-SO 2 ^{Y 4,} wherein, ^{Y 4} Represents an optionally substituted aryl group having 6 to 18 carbon atoms.), Y ² and Y ⁴ are preferably aryl groups having 6 to 10 carbon atoms. Examples of aryl groups include, but are not limited to, phenyl groups, 1-naphthyl groups, 2-naphthyl groups, indenyl groups, biphenylyl groups, anthryl groups, phenanthryl groups, and the like.

R ^{21 to} R ²³ in the general formula (B) are particularly preferably an alkyl group having 1 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a cycloalkyl group having 4 to 30 carbon atoms, and 1 to 1 carbon atoms. 30, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, benzyl, cyclohexyl Group, an isopropoxy group.

  For hydrocarbon groups having 1 to 30 carbon atoms, alkoxy groups having 1 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, amino groups, silyl groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups Substituents may be introduced.

  Examples of the substituent include an ester group, a carboxyl group, an amide group, an alkyne group, a trimethylsilyl group, an amino group, a phosphoryl group, a thio group, a carbonyl group, a nitro group, a sulfo group, an imino group, a halogeno group, and an alkoxy group. Can be mentioned. In this case, one or more substituents may be introduced at a substitutable position up to the maximum number that can be substituted, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

  Examples of the amino group which may have a substituent include, but are not limited to, an amino group, a dimethylamino group, a methylamino group, a methylphenylamino group, and a phenylamino group.

  Examples of the silyl group which may have a substituent include, but are not limited to, dimethylsilyl group, diethylsilyl group, trimethylsilyl group, triethylsilyl group, trimethoxysilyl group, triethoxysilyl group, diphenylmethyl. Examples include silyl group, triphenylsilyl group, triphenoxysilyl group, dimethylmethoxysilyl group, dimethylphenoxysilyl group, and methylmethoxyphenylsilyl group.

[(2-2) Method for producing compound B]
A compound represented by the general formula (B) having a hydrogen atom and a silylmethyl group at the same time can be synthesized with reference to the method described in International Publication No. 2008/059771. For example, a Grignard reagent having a silylmethyl group such as trimethylsilylmethylmagnesium bromide is allowed to act on fullerene in an aprotic polar solvent such as N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or pyridine. Thus, a compound having a hydrogen atom and a silylmethyl group represented by the formula (B) can be synthesized. The fullerene _can be used fullerene or its derivatives such as _{C 60} and _{C 70.}

[(2-3) Method for constructing methanofullerene structure using compound B]
In the reaction of the formula (2.1), the compound having a hydrogen atom and a silylmethyl group represented by the general formula (B) at the same time is reacted with an oxidant to produce a dihydromethano group represented by the general formula (A). Converted to.

  The type of the oxidizing agent is not particularly limited, and for example, see Non-Patent Document Chem. Rev. An oxidizing agent described in Table 2, 1996, 96, 877-910 can be used. Of these, metal salts are preferably used. As a kind of metal which forms a metal salt, transition metals, such as copper, iron, silver, nickel, manganese, are preferable. Among these, copper is particularly preferable, and as the copper salt, divalent copper salts such as copper (II) bromide, copper (II) chloride, copper (II) iodide, copper (II) triflate, and the like are more yielded. Among them, copper (II) bromide and copper (II) chloride are particularly preferable. Two or more metal salts may be used in combination.

  The equivalent amount of the oxidizing agent is usually 1 to 50 equivalents, and 3 to 10 equivalents is preferable because production costs and by-products can be suppressed and the yield can be further increased.

  Moreover, as another possible embodiment, a metal salt and an oxidizing agent other than the metal salt may be used in combination. For example, a copper salt or a metal salt composed of another metal may be used in combination with an oxidizing agent other than the metal salt. In such a case, the metal salt composed of the copper salt or other metal is necessarily required to have an oxidizing power. In addition, the equivalent weight is not limited to the above.

  In the reaction of the formula (2.1), it is preferable to use a basic compound in combination. By using a basic compound, a hydrogen atom is extracted and the oxidation reaction by an oxidizing agent can be more smoothly advanced.

  The oxidizing agent and the basic compound may be added simultaneously, or may be added in the order of the oxidizing agent and the basic compound, or in the order of the basic compound and the oxidizing agent. Preferably, it is preferable to add an oxidant after first adding a basic compound to extract a hydrogen atom to generate an anion of a fullerene compound, thereby suppressing by-products and increasing the yield.

  Although it does not specifically limit as a basic compound, Metal hydrides, such as potassium hydride or sodium hydride; Metal alkoxides, such as sodium methoxide, potassium t-butoxide, or sodium t-butoxide; Alkali metal reagents, such as n-butyl lithium An alkali metal such as lithium, sodium or potassium; or a basic organic compound such as pyridine, triethylamine, dimethylaminopyridine, or DBU. Of these, metal hydrides such as potassium hydride or sodium hydride, or metal alkoxides such as potassium t-butoxide or sodium t-butoxide are preferably used.

  Although it does not specifically limit as an equivalent of a basic compound, Usually, 0.01-100 equivalent is used with respect to a fullerene compound. Since it can suppress a by-product and can raise a yield more, Preferably it is 1-5 equivalent, More preferably, it is 1-2 equivalent, Most preferably, it is 1-1.5 equivalent.

  In the reaction of the formula (2.1), it is preferable to use a solvent in order to make the reaction proceed smoothly. There is no particular limitation on the solvent that can be used, but an ether solvent such as tetrahydrofuran; or an aromatic solvent such as benzonitrile, benzene, toluene, xylene, trimethylbenzene, chlorobenzene, or dichlorobenzene is used. Of these, aromatic solvents such as benzonitrile, benzene, toluene, xylene, trimethylbenzene, chlorobenzene and dichlorobenzene are preferable, and dichlorobenzene is particularly preferable in terms of solubility.

  The reaction temperature may be appropriately selected depending on the type of oxidizing agent, the type of solvent, etc., but is usually −78 ° C. to 300 ° C., preferably 0 ° C. to 200 ° C., more preferably 50 ° C. to It is performed in the range of 160 ° C.

  The reaction time may be appropriately selected depending on the type of oxidizing agent, the type of solvent, etc., but is usually 1 minute to 96 hours, preferably 30 minutes to 24 hours.

  In order to promote the reaction of formula (2.1), various catalysts and additives depending on various purposes may be used. The type of the catalyst or additive is not particularly limited, and may be appropriately selected according to the starting material, the type of fullerene compound to be produced (type of addition group) and the reaction conditions used.

[(2-4) Structure of Compound C]
In the general formula (C), the silylmethyl group and the other fullerene are added to the same five-membered or six-membered ring in each fullerene skeleton. The silylmethyl group and the other fullerene are usually added on the same six-membered ring, preferably in a 1,2-position or 1,4-position positional relationship, more preferably 1,4- Are in a positional relationship. Fln in the general formula (C) represents a fullerene to which an organic group may be added, and the organic group has the same meaning as the additional group R in the general formula (I).

In the general formula (C), R ^{24 to} R ²⁶ are each independently the same as R ^{21 to} R ²³ . In the two fullerenes, each of R ^{24 to} R ²⁶ may be the same or different.

[(2-5) Method for producing compound C]
The silylmethyl group-added dimer compound (fullerene dimer) represented by the general formula (C) is obtained by using a compound represented by the general formula (B) having a hydrogen atom and a silylmethyl group at the same time as a starting material. It can manufacture with a sufficient yield by the process made to react. At this time, a basic compound may be used in combination.

As the basic compound used in the production process of dimer (C), potassium t-butoxide ( ^t BuOK), potassium hydride (KH) and the like can be suitably used, and the addition amount is a starting material. The range of 1-10 equivalent is preferable with respect to the fullerene compound which has a silylmethyl group.

The oxidizing agent used in the production process of the dimer (C) is not particularly limited, and various oxidizing agents can be used. N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), iodine (I ₂ ) A halogen-based oxidant such as oxygen and oxygen (O ₂ ) can be preferably used. Although there is no restriction | limiting in particular as addition amount, 1-100 equivalent is preferable with respect to the fullerene compound which has a silylmethyl group, and the range of 1-10 equivalent is further more preferable.

  The reaction in the production process of dimer (C) may be any of a closed system, an open system, and a gas flow system. Further, the reaction method is not particularly limited, and can be appropriately selected in consideration of the types of fullerenes, fullerene compounds, basic compounds and oxidizing agents to be used, and their amounts.

  The reaction in the production process of the dimer (C) is preferably performed using a solvent. As the solvent, for example, toluene, tetrahydrofuran, dichlorobenzene, or a mixed solvent thereof is used, and among these, dichlorobenzene is preferably used as the solvent.

  In order to accelerate the reaction in the production process of the dimer (C), various additives according to various purposes may be used. The type of the catalyst or additive is not particularly limited, and may be appropriately selected depending on the starting material and the type of fullerene compound to be produced (type of addition group).

  The order of addition and addition method of the fullerene compound having a silylmethyl group, a basic compound, and an oxidizing agent to the reaction vessel, which are starting materials for the reaction in the production process of dimer (C), are arbitrary, but the solvent in which the fullerene compound is dissolved It is preferable to add a basic compound to the mixture, and then add an oxidizing agent. Specifically, after a fullerene compound having a silylmethyl group is mixed with a solvent, a basic compound is used to deprotonate to generate anions, and then an oxidant is added to produce a fullerene dimer. It is preferable.

  The deprotonation reaction using the basic compound in the production process of dimer (C) is usually −70 ° C. to 70 ° C., preferably −50 ° C. to 50 ° C., for several minutes to 2 hours, preferably It takes about 5 minutes to 1 hour.

  The oxidation reaction using an oxidizing agent in the production process of dimer (C) is usually −70 ° C. to 70 ° C., preferably −50 ° C. to 50 ° C., for several minutes to 4 hours, preferably 5 minutes. ~ 2 hours.

  The fullerene dimer produced by the reaction does not need to be purified when the selective production rate is high. However, the fullerene dimer can be arbitrarily isolated and purified by the same method as in the first step. However, since it may be obtained as a crude product mixed with by-products such as remaining raw materials and oxides, a dimer compound having a predetermined silylmethyl group added can be isolated and purified from the crude product. .

  As a technique for isolating and purifying the produced fullerene compound, a technique by chromatography such as HPLC or column chromatography, a technique of solvent extraction using an organic solvent or the like, or recrystallization or reprecipitation may be mentioned. Even when by-products are produced, it is not always necessary to purify and isolate the dimer compound. The obtained crude product is used as it is in the next step of the reaction of the formula (2.2), derivatized into a compound having a dihydromethano group represented by the general formula (A), and then isolated and purified. be able to. Alternatively, the compound derived from (A) can be further derivatized and then isolated and purified.

Using two or more fullerene compounds having different substituents R ^{21 to} R ²³ , dimers having different R ^{24 to} R ²⁶ in the two fullerenes can be produced.

[(2-6) Method for constructing methanofullerene structure using compound C]
In the reaction of the formula (2.2), the kind of the oxidizing agent, the equivalent amount of the oxidizing agent, the solvent, the reaction temperature, the reaction time, the catalyst, the additive and the like are the same as those in the reaction in the formula (2.1). That is, a metal salt can be suitably used as the oxidizing agent. In particular, it is preferable to use a divalent copper salt from the viewpoint of reactivity. However, unlike the case of the formula (2.1), it is not particularly necessary to use a basic compound in the reaction of the formula (2.2). Thus, by allowing an oxidizing agent to act on compound C, compound C can be cleaved to obtain a methanofullerene compound having a dihydromethano structure.

[(2-7) Comparison of Method for Constructing Methanofullerene Structure from Compound B and Method for Constructing from Compound C]
The method for producing a methanofullerene compound represented by the method of formula (2.2) has a slightly higher reaction yield of dihydromethano group than the method of formula (2.1). When the yield of the step of obtaining C) is high, it is preferable in that the total yield becomes high. On the other hand, since the method for producing a methanofullerene compound represented by the method of formula (2.1) does not need to go through a step of obtaining a silylmethyl group-added dimer compound (C), the steps required for production are short. preferable.

[(2-8) Specific production example of methanofullerene compound according to this embodiment]
Using the above-mentioned method for forming a dihydromethano group, the methanofullerene compound (I) according to this embodiment can be synthesized as follows.

  That is, as one method, a dihydromethanofullerene (AI) is synthesized from a fullerene compound (BI) having both a hydrogen atom and a silylmethyl group according to the following formula using the reaction of the formula (2.1). To do.

または、ダイマー化合物（Ｃ−Ｉ）から、式（２．２）の反応を用いて、以下の式に従ってジヒドロメタノフラーレン（Ａ−Ｉ）を合成する。（Ｃ−Ｉ）において、２つのフラーレンの各々のＲ^２４〜Ｒ^２６は、同一であってもよいし、異なっていてもよい。

Alternatively, dihydromethanofullerene (AI) is synthesized from dimer compound (CI) according to the following formula using the reaction of formula (2.2). In (CI), R ^{24 to} R ²⁶ of each of the two fullerenes may be the same or different.

  The methanofullerene compound according to this embodiment can be synthesized by introducing an additional group to the produced dihydromethanofullerene (AI). The introduction of an additional group into the fullerene compound will be described later.

As another method, from the fullerene compound (B-II) having a hydrogen atom, a silylmethyl group and an additional group R at the same time, using the reaction of the formula (2.1), the methanofullerene according to this embodiment according to the following formula Compounds may be synthesized. As described above, fln may have an additional group R in the following formula. In the following formula, m ′ ″ is preferably 1 or 2, m ′ is preferably 0 or 1, m ″ is preferably 1 or 2, and m ′ ″ is m. It is the sum of 'and m''.

Alternatively, the methanofullerene compound according to this embodiment may be synthesized from the dimer compound (C-II) according to the following formula using the reaction of the formula (2.2). In (C-II), R ^{24 to} R ²⁶ and the additional group R of each of the two fullerenes may be the same or different. In the following formula, m ′ is preferably 0 or 1, and m ′ ″ = m ′ + 1.

  Below, the method to introduce | transduce an addition group with respect to a fullerene compound is demonstrated. The method for introducing the additional group R into the fullerene compound is not particularly limited, and a known method can be referred to. For example, the formation of an addition group represented by the general formula (n1) is described in International Publication No. 2008/059771 and J. Org. Am. Chem. Soc. , 2008, 130 (46), 15429-15436. For example, a method using a Grignard reagent as described in “(2-2) Production method of compound B” can be applied.

  Formation of an addition group represented by the general formula (n2) is described in J. Org. 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.

  Formation of the addition group represented by the general formula (n3) is described in Angew. Chem. Int. Ed. Engl. 1993, 32, 78-80, JP-T-8-505859, Chemical Review 1999, 99, 3199-3246, Tetrahedron Lett. 1997, 38, 285-288, International Publication No. 2008/018931 and International Publication No. 2009/086212 can be implemented with reference to known documents.

  Formation of an addition group represented by the general formula (n4) is described in J. Org. Chem. Soc. Perkin Trans. 1, 1997, 1595, Thin Solid Films, 2005, 489, 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. For example, a structure such as formula (n4) can be introduced by reacting a fullerene compound with hydrazone.

  Formation of the addition group represented by the general formula (n5) is described in J. Org. Org. Chem. 2007, 72, 2538-2542, Organic & Biomolecular Chemistry 2004, 2, 1160-1163, Organic & Biomolecular Chemistry 2003, 1, 2604-2611, Org. Lett. 2003, 5, 2239-2242, J. MoI. Org. Chem. 2002, 67, 5946-5952, and Tetrahedron Lett. 1996, 37, 2049-2052.

  Formation of the addition group represented by the general formula (n6) is described in Org. Lett. 2006, 8, 3203-3205, Org. Lett. It can be implemented by publicly known documents described in 2009, 11, 1507-1510.

  Formation of an addition group represented by the general formula (n7) is described in J. Org. Am. Chem. Soc. 1993, 115, 11024-11025. For example, a structure such as formula (n7) can be introduced by cycloaddition of a fullerene compound and an alkyne.

[(3) Film forming method]
In order to form a film of the methanofullerene compound according to the present embodiment, a method of forming a film by a vapor deposition method and a method of forming a film by coating can be employed. In view of process performance including ease and cost, it is preferable to use a coating method. Therefore, it is more preferable to use a methanofullerene compound that can be formed by a coating method. In order to enable the coating method, it is preferable that the methanofullerene compound itself can be applied in a liquid state, or that the methanofullerene compound is highly soluble in some solvent and can be applied as a solution. The methanofullerene compound in this embodiment has high solvent solubility and is suitable for film formation by a coating method.

  The solvent used when forming the methanofullerene compound of the present embodiment is not particularly limited, but a non-halogen solvent is preferable. Halogenous solvents such as chloroform, chlorobenzene and dichlorobenzene are also possible, but alternatives are required in terms of environmental impact. Examples of non-halogen solvents include non-halogen aromatic hydrocarbons. Among these, toluene, xylene, cyclohexylbenzene, tetralin and the like are preferable. Alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, ether solvents such as dimethoxyethane and tetrahydrofuran, and ester solvents such as ethyl acetate, butyl acetate and methyl lactate An amide solvent such as a solvent, dimethylformamide, dimethylacetamide or the like may be used. These solvents can be used alone or mixed with the above aromatic hydrocarbons at an arbitrary ratio.

  The solubility of the methanofullerene compound in the solvent is usually 0.3% by weight or more, preferably 1.0% by weight or more, more preferably, when toluene is used as the solvent at room temperature (25 ° C.). It is 1.2% by weight or more, more preferably 2.5% by weight or more, and particularly preferably 4.0% by weight or more. On the other hand, it is usually 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less. When the solubility is 0.5% by weight or more, the dispersion stability of the methanofullerene compound is improved, and aggregation, sedimentation, separation, and the like tend not to occur.

[(2-9) Advantages of the method for producing a methanofullerene compound according to this embodiment]
The methanofullerene compound according to the present embodiment generates a dihydromethanofullerene (A-1) by introducing a dihydromethanofullerene into a fullerene and introduces an additional group R according to the method according to the present embodiment. Can be manufactured. As another method, the methanofullerene compound according to the present embodiment can be produced by forming a dihydromethano group according to the present embodiment with respect to the fullerene compound into which the additional group R is introduced.

  Although a dihydromethano group can be introduced into the fullerene compound by a known method, the method according to this embodiment has the following advantages. That is, in this method, since the reaction yield is high, the manufacturing cost can be suppressed. In this method, the number of dihydromethano groups formed can be easily controlled by controlling the number of silylmethyl groups contained in the (B) or (C) silylmethyl group-added fullerene compound. For this reason, it is not necessary to remove by-products having different numbers of addition of dihydromethano groups, and purification and isolation are facilitated. For example, if there is one silylmethyl group introduced into one fullerene ring at the time of the silylmethyl group-added fullerene compound (B) or (C), the methanofullerene compound obtained from this silylmethyl group-added fullerene compound Is considered to have one dihydromethano group. As an example, by purification, a silylmethyl group-added fullerene compound (B) or (C) in which one silylmethyl group is introduced into one fullerene ring can be obtained with high purity. Thus, the methanofullerene compound in which one dihydromethano group is introduced by passing through the silylmethyl group-added fullerene compound (B) or (C) in which one silylmethyl group is introduced into one fullerene ring ( A) can be obtained with high purity.

  Further, in the case of a known method in which fullerene or a derivative thereof is directly dihydromethanoized without going through a silylmethyl group adduct, it is often difficult to remove the fullerene or the derivative as a raw material. On the other hand, in the method via the silylmethyl group-added fullerene compound of the present application, since the fullerene or its derivative as a raw material can be removed at the time of purification of the silylmethyl group-added fullerene compound of (B) or (C), This makes it easy to purify and isolate the methanofullerene compound. Such an effect can be further enhanced by devising a substituent on the silylmethyl group.

  In addition, since this method does not require the use of ultrasonic waves or electrochemical techniques, it is excellent for large scale or industrial applications.

<1.1.2 p-type semiconductor compound>
The p-type semiconductor compound is not particularly limited, but a low molecular material or a high molecular material can be used.

The polymer material is not particularly limited. Conjugated polymer semiconductors such as polythiophene, polyfluorene, polyphenylene vinylene, polythienylene vinylene, polyacetylene, polyaniline; polymer semiconductors such as oligothiophene substituted with alkyl groups or other substituents Can be mentioned. Moreover, the semiconductor polymer which copolymerized 2 or more types of monomer units is also mentioned. Conjugated polymers 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 polymers described in known literature such as 2002, 74, 2031-3044, Handbook of THIOPHENE-BASED MATERIALS (2 volumes), 2009, and derivatives thereof, or polymers that can be synthesized by a combination of the described monomers. Can do. Polymer or monomer substituents can be selected to control solubility, crystallinity, film-forming properties, HOMO level, LUMO level, and the like.

  A polymer material soluble in an organic solvent is preferable because a coating method can be used in the manufacturing process of the organic solar cell element. In addition, the above kind of compound or a mixture of plural kinds of compounds may be used. The polymer material may have any self-organized structure in the film-formed state, or may be in an amorphous state.

  There is no particular limitation on the low molecular weight material. The molecular weight of the low molecular weight material is not particularly limited, but is usually 100 or more, preferably 200 or more, and is usually 5000 or less, preferably 2000 or less. The low molecular weight material is preferably crystalline. The reason is that the p-type semiconductor compound having crystallinity has a strong intermolecular interaction, and efficiently transports holes generated at the mixed layer interface between the p-type semiconductor compound and the n-type semiconductor compound in the active layer to the positive electrode. This is because it is expected to be possible.

The crystallinity in the present embodiment is a property of a compound that takes a three-dimensional periodic arrangement in which the orientation is aligned by intermolecular interaction or the like. Examples of the crystallinity measuring method include X-ray diffraction (XRD), field effect mobility measurement, and the like. In particular, in the field effect mobility measurement, a crystalline compound having a hole mobility of 1.0 × 10 ⁽⁻⁵⁾ cm ² / (Vs) or more is preferable, and 1.0 × 10 ⁽⁻⁴⁾ cm ² / ( Vs) or higher is more preferred.

  The low molecular weight material is not particularly limited as long as the above performance is satisfied. Specifically, the low molecular weight material is a condensed aromatic hydrocarbon such as naphthacene, pentacene, or pyrene; and an oligo molecule including four or more thiophene rings such as α-sexithiophene. Thiophenes; thiophene ring, benzene ring, fluorene ring, naphthalene ring, anthracene ring, thiazole ring, thiadiazole ring, benzothiazole ring combined in total; phthalocyanine compound and metal complex thereof, and porphyrin compound such as tetrabenzoporphyrin And macrocyclic compounds such as metal complexes thereof. A phthalocyanine compound and a metal complex thereof, or a porphyrin compound such as tetrabenzoporphyrin and a metal complex thereof are preferable.

  Examples of the porphyrin compound and its metal complex (Q in the figure are CH), the phthalocyanine compound and its metal complex (Q is N) used as the p-type semiconductor compound 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, 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. Among them, preferred is a saturated or unsaturated chain hydrocarbon group having 1 to 12 carbon atoms, or a saturated or unsaturated cyclic hydrocarbon.

  Among the phthalocyanine compounds and metal complexes thereof, 29H, 31H-phthalocyanine, copper phthalocyanine complex, zinc phthalocyanine complex, titanium phthalocyanine oxide complex, magnesium phthalocyanine complex, lead phthalocyanine complex, copper 4,4 ′, 4 ″, 4 '' '-Tetraaza-29H, 31H-phthalocyanine complex, more preferably 29H, 31H-phthalocyanine, copper phthalocyanine complex. 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), 29H, 31H-tetrabenzo [b, g, l, q] porphine vanadium (IV) oxide And more preferably 5,10,15,20-tetraphenyl-21H, 23H-porphine, 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 the p-type semiconductor compound, it is desirable to use a porphyrin compound and / or a polymer semiconductor. The HOMO level of the p-type semiconductor compound is not particularly limited, but the HOMO level of the p-type semiconductor compound combined with the above methanofullerene compound is usually −5.7 eV or more, more preferably −5.5 eV or more. It is preferably −4.6 eV or less and −4.8 eV or less. When the p-type semiconductor compound has a HOMO level of −5.7 eV or higher, the characteristics of the p-type semiconductor are improved, and when the p-type semiconductor compound has a HOMO level of −4.6 eV or lower, the stability of the compound is improved. As a result, the open circuit voltage (Voc) is improved. The LUMO level of the p-type semiconductor compound is not particularly limited, but the LUMO level of the p-type semiconductor compound combined with the above methanofullerene compound is usually −3.7 eV or higher, preferably −3.5 eV or higher. 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 compound 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 compound is −3.7 eV or more, electron transfer to the n-type semiconductor easily occurs and the short-circuit current density is improved.

[Semiconductor compound precursor]
When using a low molecular weight material as the p-type semiconductor compound, in addition to the method of forming a semiconductor layer by vapor deposition, the semiconductor compound precursor is converted into a semiconductor after the semiconductor compound precursor layer is formed, for example, by coating. Thus, there is a method for forming a semiconductor layer. The semiconductor compound precursor according to the present embodiment is converted into a semiconductor compound by changing the chemical structure of the semiconductor compound precursor by applying an external stimulus such as heating or light irradiation to the semiconductor compound precursor. Is.

  In addition, the semiconductor compound precursor according to the present embodiment is preferably excellent in film formability. In particular, in order to be able to apply the coating method, the semiconductor compound precursor itself can be applied in a liquid state, or the semiconductor compound precursor can be applied as a solution with high solubility in some solvent. It is preferable. If the suitable range of solubility is raised, the solubility with respect to the solvent of a semiconductor compound precursor will be 0.1 weight% or more normally, Preferably it is 0.5 weight% or more, More preferably, it is 1 weight% or more.

  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, decane; toluene, xylene Aromatic hydrocarbons such as chlorobenzene and orthodichlorobenzene; lower alcohols such as methanol, ethanol and propanol; ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; esters such as ethyl acetate, butyl acetate and methyl lactate Halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane, trichloroethylene; ethers such as ethyl ether, tetrahydrofuran, dioxane; dimethylformamide, dimethylacetate Amides such as amides. Among them, preferred are aromatic hydrocarbons such as toluene, xylene, chlorobenzene and orthodichlorobenzene, and halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane and trichloroethylene.

  Furthermore, it is preferable that the semiconductor compound precursor according to the present embodiment can be easily converted into a semiconductor compound. In the step of converting a semiconductor compound precursor to a semiconductor compound, which will be described later, what kind of external stimulus is given to the semiconductor precursor is arbitrary, but 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 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 the semiconductor compound precursor which concerns on this embodiment is converted into a semiconductor compound with a high yield through a conversion process. Under the present circumstances, the yield of the semiconductor compound obtained by converting from a semiconductor compound precursor is arbitrary unless the performance of an organic photoelectric conversion element is impaired. If the suitable range of a yield is raised, the yield of the semiconductor compound obtained from a semiconductor compound precursor is so preferable that it is high, and is 90 mol% or more normally, Preferably it is 95 mol% or more, More preferably, it is 99 mol% or more.

The semiconductor compound precursor according to the present embodiment is not particularly limited as long as the semiconductor compound precursor has the above characteristics, but as a specific semiconductor compound precursor, a compound described in JP-A-2007-324587 can be used. Among these, a preferable example includes a compound represented by the following formula (D1).

In the formula (D1), at least one of X ¹ and X ² represents a group that forms a π-conjugated divalent aromatic ring, and Z ¹ -Z ² represents a group that can be removed by heat or light. The π-conjugated compound obtained by elimination of Z ¹ -Z ² is preferably 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 (D1), Z ¹ -Z ² is eliminated by heat or light as shown in the following chemical reaction formula, and a highly planar π-conjugated compound (D2) is generated. From the semiconductor compound precursor according to the present embodiment, a π-conjugated compound that is a semiconductor compound is thus obtained.

  Examples of the compound represented by the formula (D1) include the following. T-Bu represents a t-butyl group. M represents a divalent metal atom or an atomic group in which a trivalent or higher metal and another atom are bonded.

  For example, specific examples of converting the semiconductor compound precursor include the following.

<1.2 Buffer layer (130, 150)>
The photoelectric conversion element of this embodiment can have one or more buffer layers as described above. The buffer layer can be classified into a hole extraction layer 130 and an electron extraction layer 150. The electron extraction layer 150 can be provided between the active layer 140 and the electrode (negative electrode) 160. The hole extraction layer 130 can be provided between the active layer 140 and the electrode (positive electrode) 120.

<1.2.1 Electron Extraction Layer (150)>
The material of the electron extraction layer 150 is not particularly limited as long as it can improve the efficiency of extracting electrons from the active layer 140 to the negative electrode 160, but broadly includes inorganic compounds and organic compounds. As the electron extraction layer, either material may be used as a single layer, or these materials may be laminated.

As an inorganic compound material used for the electron extraction layer, an alkali metal salt such as Li, Na, K, or Cs, or an n-type oxide semiconductor such as titanium oxide (TiO _x ) 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 conceivable to reduce the work function of the cathode in combination with an electron extraction electrode (cathode) such as Al and increase the voltage applied to the inside of the solar cell element.

  Alkali metal salts can be formed by vacuum deposition such as vacuum deposition or sputtering, but it is desirable to form them by vacuum deposition using resistance heating. This is because damage to the underlying organic layer can be reduced. The film thickness is usually 0.1 nm or more, on the other hand, usually 50 nm or less, preferably 20 nm or less. If it is too thin, the effect of the electron extraction layer is not sufficient, and if it is too thick, it acts as a series resistance component, so that the device characteristics tend to be impaired.

  For the film formation of titanium oxide TiOx, vacuum film formation such as sputtering can be used, but film formation by a coating method is desirable. For example, Adv. Mater. 18, 572 (2006). The film thickness is usually 0.1 nm or more, preferably 0.5 nm or more, more preferably 1 nm or more, and is usually 1 μm or less, preferably 100 nm or less, more preferably 50 nm or less.

  A vacuum film formation such as a sputtering method can also be used for the film formation of zinc oxide ZnO, but a film formation by a coating method is desirable. For example, Sol-Gel Science, C.I. J. et al. Brinker, G.M. W. It can be formed by the sol-gel method described in Scherer, Academic Press (1990). The film thickness is usually 0.1 nm or more, preferably 2 nm or more, more preferably 5 nm or more, and is usually 1 μm or less, preferably 100 nm or less, more preferably 50 nm or less.

Specific examples of the organic compound material used for the electron extraction layer include bathocuproine (BCP) or bathophenanthrene (Bphen), (8-hydroxyquinolinato) aluminum (Alq ₃ ), boron compound, oxadiazole compound, Examples include benzimidazole compounds, naphthalenetetracarboxylic anhydride (NTCDA), perylenetetracarboxylic anhydride (PTCDA), phosphine oxide compounds, and phosphine sulfide compounds.

  Among them, a phosphine oxide compound substituted with an aryl group and a phosphine sulfide compound substituted with an aryl group are preferable, and a triaryl phosphine oxide compound, a triaryl phosphine sulfide compound, and two diaryl phosphine oxide units are more preferable. Aromatic hydrocarbon compounds having the above, aromatic hydrocarbon compounds having two or more diarylphosphine sulfide units, triarylphosphine oxide compounds substituted with fluorine atoms or perfluoroalkyl groups, and aromatics having two or more diarylphosphine oxide units Group hydrocarbon compound. In addition to the above materials, alkali metal or alkaline earth metal may be doped.

  The film thickness of the electron extraction layer 150 is not particularly limited, but is usually 0.01 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 150 is 0.01 nm or more, it functions as a buffer material. When the film thickness of the electron extraction layer 150 is 40 nm or less, electrons are easily extracted, and photoelectric conversion is performed. Efficiency is improved.

<1.2.2 Hole Extraction Layer (130)>
The material of the hole extraction layer 130 is not particularly limited as long as the hole extraction efficiency from the active layer 140 to the positive electrode 120 can be improved. Specific examples thereof include conductive organic compounds such as polythiophene, polypyrrole, polyacetylene, and triphenylenediamine. A thin film made of a metal such as Au, In, Ag, or Pd 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 130 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 is 2 nm or more, the film functions as a buffer material. When the film thickness of the hole extraction layer is 40 nm or less, holes are easily extracted, and the photoelectric conversion efficiency Will improve.

<1.3 Electrodes (120, 160)>
The electrode according to the present embodiment has a function of collecting holes and electrons generated by light absorption. The electrode of this embodiment is composed of a pair of positive electrode 120 and negative electrode 160. The positive electrode 160 is preferably an electrode suitable for collecting holes. The negative electrode 160 is preferably an electrode suitable for collecting electrons. 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.

  An electrode suitable for collecting holes is a conductive material generally having a higher work function than that of the negative electrode, and is an electrode having a function of smoothly extracting holes generated in the active layer. In the present embodiment, the positive electrode 120 is adjacent to the hole extraction layer 130. Examples of the material of the positive electrode 120 include conductive metal oxidation such as nickel oxide, tin oxide, indium oxide, indium tin oxide (ITO), indium-zirconium oxide (IZO), titanium oxide, indium oxide, and zinc oxide. Metal, gold, platinum, silver, chromium, cobalt and the like, or alloys thereof.

  Since these substances have a high work function, they are preferable, and further, a conductive polymer material represented by PEDOT / PSS in which a polythiophene derivative is doped with polystyrene sulfonic acid can be laminated. When such a conductive polymer is laminated, since the work function of the conductive polymer material is high, it is suitable for a negative electrode such as Al or Mg, even if it is not a material having a high work function as described above. Metals can also be widely used. PEDOT / PSS doped with polystyrene sulfonic acid in a polythiophene derivative, or a conductive polymer material doped with iodine or the like in polypyrrole, polyaniline, or the like can also be used as the positive electrode material.

  Further, when the positive electrode 120 is a transparent electrode, it is preferable to use a conductive metal oxide having translucency such as ITO, zinc oxide, and tin oxide, and ITO is particularly preferable. The film thickness of the positive electrode 120 is not particularly limited, but is usually 10 nm or more, preferably 20 nm or more, more preferably 50 nm or more, and is usually 10 μm or less, preferably 1 μm or less, more preferably 500 nm or less. When the film thickness of the positive electrode 120 is 10 nm or more, sheet resistance is suppressed, and when the film thickness of the positive electrode 120 is 10 μm or less, light can be efficiently converted into electricity without a decrease in 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 positive electrode 120 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.

  Examples of the method for forming the positive electrode 120 include a vacuum film formation method such as vapor deposition and sputtering, and a method of forming a film by applying an ink containing nanoparticles and a precursor.

  An electrode suitable for collecting electrons is generally a conductive material having a work function higher than that of the positive electrode, and has a function of smoothly extracting electrons generated in the active layer. In this embodiment, the negative electrode 160 is adjacent to the electron extraction layer 150.

  Examples of the material of the negative electrode 160 include metals such as platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, cesium, calcium and magnesium, and alloys thereof, fluoride Examples thereof include inorganic salts such as lithium and cesium fluoride, and 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 positive electrode 120, the negative electrode 160 can also be made of a material having a high work function suitable for the positive electrode by using an n-type semiconductor compound such as titania having conductivity for the electron extraction layer 150. From the viewpoint of electrode protection, the negative electrode 160 is preferably made of a metal such as platinum, gold, silver, copper, iron, tin, aluminum, calcium and indium, or an alloy using these metals.

  The thickness of the negative electrode 160 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 500 nm or less, more preferably 1 μm 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 negative electrode 160 is 10 nm or more, sheet resistance is suppressed, and when the film thickness of the negative electrode 160 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 negative electrode 160 is not particularly limited, but is 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. As a method for forming the negative electrode 160, there are a vacuum film formation method such as vapor deposition and sputtering, and a method of forming a film by applying an ink containing nanoparticles and a precursor.
Further, the positive electrode 120 or the negative electrode 160 may be laminated in two or more layers, and characteristics (electric characteristics, wetting characteristics, etc.) may be improved by surface treatment.

  After laminating the positive electrode 120 and the negative electrode 160, it is preferable to heat the laminate in a temperature range of usually 50 ° C or higher, preferably 80 ° C or higher, and usually 280 ° C or lower, preferably 250 ° C or lower. 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. By this heat treatment, an effect of improving the thermal stability of the obtained photoelectric conversion element and improving the adhesion between the electrode and the buffer layer can be obtained. This annealing treatment is also effective for self-organization of the active layer.

<1.4 Substrate>
The photoelectric conversion element 100 according to the present embodiment has a substrate 110 that is normally a support. That is, the electrodes 120 and 160, the active layer 140, and the buffer layers 130 and 150 are formed on the substrate 100. The material of the substrate 110 (substrate material) is arbitrary as long as the effects of the present embodiment are not significantly impaired. Preferable 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 and polyethylene, cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, epoxy resin and other organic materials; paper, synthetic paper and other paper materials; 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 a board | substrate, For example, shapes, such as a board, a film, a sheet | seat, can be used. There is no limitation on the thickness of the substrate. However, it is preferably 5 μm or more, especially 20 μm or more, and usually 20 mm or less, especially 10 mm or less. If the substrate is too thin, the strength of the photoelectric conversion element may be insufficient, and if the substrate is too thick, the cost may be increased or the weight may be increased. In the case where the substrate is glass, if it is too thin, the mechanical strength is reduced and the substrate is liable to break. Therefore, the thickness is preferably 0.01 mm or more, more preferably 0.1 mm or more. Moreover, since weight will become heavy when too thick, Preferably it is 1 cm or less and 0.5 cm or less.

<2. Solar cell module>
The photoelectric conversion element according to the present invention is preferably used as a solar cell element. In particular, the photoelectric conversion element according to the present invention is preferably used as a solar cell element in a solar cell (or a solar cell module). Furthermore, the photoelectric conversion element according to the present invention can be suitably used as a solar cell element in a thin film solar cell. FIG. 2 is a cross-sectional view schematically showing the configuration of a thin film solar cell as one embodiment of the present invention. The thin film solar cell shown in FIG. 2 is only an example of the solar cell according to the present invention. It will be apparent to those skilled in the art that the solar cell according to the present invention can have a different configuration than that shown in FIG. For example, some of the components shown in FIG. 2 may not be present, or may be replaced with another element having the same kind of function. Further components may also be added to the solar cell shown in FIG.
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 in this order, and further a sealing material 11 that seals the edges of the weatherproof protective film 1 and the back sheet 10. I have. 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. .

<2.1 Weatherproof 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, erosion caused by wind and rain, and the like. 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 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, it is suitable as a surface covering material for the thin-film solar cell 14 such as weather resistance, heat resistance, transparency, water repellency, stain resistance, and mechanical strength. It is preferable that it has a good performance and has the property of maintaining 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 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.

<2.2 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 and 9 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, so that the solar cell element 6 and, if necessary, the gas barrier films 3, 9 etc. 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 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. 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, and 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 adhesion of foreign matters etc. by a fine bubble, the repelling in a drying process, etc. are suppressed. Known surfactants (cationic surfactants, anionic surfactants, nonionic surfactants) can be used as the surfactant. Among these, a silicon-based surfactant or a fluorine-based surfactant is 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.).

  The ultraviolet cut film 2 may be formed of one kind of material or may be formed of two or more kinds 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.

<2.3 Gas barrier film (3)>
[2.3.1 Configuration of gas barrier film]
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. Two examples of the configuration of the gas barrier film 3 are preferable. 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.

[2.3.2 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 plastic film base material 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) and biaxially stretched polyethylene naphthalate (PEN) are preferably used as a plastic film substrate because they are excellent in thermal dimensional stability.

  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 these, a combination of at least one of a polyester resin, a urethane resin, and an acrylic resin and at least one of an oxazoline group-containing resin, a carbodiimide group-containing resin, an epoxy group-containing resin, and an isocyanate group-containing 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 electric discharge treatment before application of the anchor coating agent. Good.

[2.3.3 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, nitrides, and oxynitrides. 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.

  Moreover, when an inorganic barrier layer is comprised from 2 or more types of metal oxides, it is desirable to contain aluminum oxide and silicon oxide as a metal oxide. Among them, when the inorganic barrier layer is made of aluminum oxide and silicon oxide, the ratio of aluminum to 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.

[2.3.4 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), polyamide (diolefin / diamide) and the like.

  (Iv) Examples include acrylate monomers. The acrylate monomer includes monofunctional, bifunctional, and polyfunctional acrylate monomers, and any of them may be used. However, in order to obtain an appropriate evaporation rate, degree of cure, cure rate, and the like, 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, carboxy group-containing acrylate monomers, and the like. 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, a polyfunctional oligomer etc. are mentioned, for example. Examples of the oxetane 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, and 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 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; radiation heating with infrared rays, microwaves or the like; 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, and sunlight irradiation light. 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 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.

[2.3.5 Particularly Suitable Gas Barrier Film]
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. Then, the edges of the gas barrier films 3 and 9 are sealed with the sealing material 11, and the solar cell elements 6 are placed in the space surrounded by the gas barrier films 3 and 9 and the sealing material 11, so that the solar cell elements 6 It can be protected from oxygen. 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. .

<2.4 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, when the solar cell element 6 is covered with the gas barrier film 3 or the like, the getter material film 4 absorbs moisture that slightly enters the space formed by the gas barrier films 3 and 9 and the sealing material 11. Can be captured and 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 getter material film 4 absorbs oxygen, when the solar cell element 6 is covered with the gas barrier films 3, 9, etc., it slightly enters the space formed by the gas barrier films 3, 9 and the seal material 11. Oxygen is captured by the getter material film 4 and the influence of the oxygen on the solar cell element 6 can be eliminated.

  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, alkaline earth metal oxide, alkali metal or alkaline earth metal hydroxide, silica gel, zeolite compound, magnesium sulfate as a substance that absorbs moisture. 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, an aluminum metal complex, etc. are also mentioned. 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.

  If the getter material film 4 is in the space formed by the gas barrier films 3, 9 and the sealing material 11, the formation position is not limited. However, the front surface of the solar cell element 6 (the surface on the light receiving surface side. Side surface) and the back surface (surface opposite to the light receiving surface; upper surface in FIG. 2) are preferably covered. 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 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. .

  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 of attaching a film in which the water-absorbing agent or desiccant is dispersed with an adhesive, water-absorbing agent or desiccant A method of applying the solution by a spin coating method, an inkjet method, a dispenser method, or the like can be used. 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, and the like can be used. Among these, films of polyethylene resin, fluorine resin, cyclic polyolefin resin, and polycarbonate resin are preferable. In addition, the said resin may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

<2.5 Sealant (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 the 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 an organic peroxide include 2,5-dimethylhexane; 2,5-dihydroperoxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; 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 silane coupling agents used for this purpose include γ-chloropropyltrimethoxysilane; vinyltrichlorosilane; vinyltriethoxysilane; vinyl-tris- (β-methoxyethoxy) silane; γ-methacryloxypropyltri Methoxysilane; β- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. 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 and 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; methyl hydroquinone. 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. Further, when used for a long period of 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-based 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: A soft propylene-type copolymer is 30 weight part or more, Preferably it is 50 weight part or more, and is 100 weight part or less normally, Preferably it is 90 weight part 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 a preferred range, 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 component 1 and component 2 are blended has a melt flow rate (ASTM D 1238, 230 degrees, load 2.16 kg) of 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 were compounded 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 and 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.

  These are usually 0.1 parts by weight or more, usually 5 parts by weight or less, preferably 100 parts by weight of the silane coupling agent, based on 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 that 0.1 to 5 parts by weight of the coupling agent is included with respect to 100 parts by weight of the thermoplastic resin composition (total amount of component 1 and component 2). Even if a silane-grafted thermoplastic resin composition is used, the same or better adhesiveness as that of the silane coupling agent blend can be obtained for glass and 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). Part or more, and 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. Examples of the copolymer include 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.

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, the solar cell element 6 is not adversely affected, and has good heat resistance, mechanical strength, flexibility (solar cell sealing property), and transparency. Have sex. Further, since no material cross-linking step is required, the manufacturing time of the thin film solar cell 100 during sheet molding can be greatly reduced, 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.

<2.6 Solar cell element (6)>
As the solar cell element 6, the above-described photoelectric conversion element can be used.

-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.

<2.7 Sealant (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.

<2.8 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. Examples of such absorbents include CaO, BaO, Zr-Al-BaO as moisture absorbents, and activated carbon, molecular sieves, etc. as oxygen absorbents.

<2.9 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.

<2.10 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 and sheets having excellent strength and weather resistance, heat resistance, water resistance, and 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 Resins, poly (meth) acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate or polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyamideimide resins, polyarylphthalate resins Sheet of various resins such as silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin, etc. It is possible to use. 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 vinylidene fluoride resin. (PVDF), vinyl fluoride resin (PVF) and the like. 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, a vapor deposition film of an inorganic oxide is provided on one side or both sides of the base film, and further, heat resistance is provided on both sides of the base film provided with the vapor deposition film of the inorganic oxide. 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, oxygen and the like.

  Basically, as the base film, various resin films having excellent close adhesion with an inorganic oxide vapor deposition film, etc., excellent strength, weather resistance, heat resistance, water resistance, and light resistance are used. 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 Resins, poly (meth) acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate or polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyamideimide resins, polyaryl phthalate resins Silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulosic resin, etc. It is possible to use. 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 described above, for example, a film of a fluorine resin such as polytetrafluoroethylene (PTFE), vinylidene fluoride resin (PVDF), or vinyl fluoride resin (PVF) is used. More preferably it is used. Further, among the fluororesin films, in particular, a fluororesin film (PVF); a fluororesin film made of 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, 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.

As the inorganic oxide vapor-deposited film, basically any thin film on which a metal oxide is vapor-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.

  As the polypropylene resin, for example, a homopolymer of propylene; a copolymer of propylene and another monomer (for example, α-olefin) can be used. Moreover, an isotactic polymer can also be used as a polypropylene resin. The melting point of the polypropylene resin is usually 164 ° C. to 170 ° C., the specific gravity is usually 0.90 to 0.91, and the molecular weight is usually 100,000 to 200,000.

  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.

  When a polypropylene resin film is laminated on the base film, a laminating adhesive 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, and 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 heat melting type, and a hot pressure type. The adhesive can be applied by 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. As the amount of ^{coating, 0.1g / m 2 ~10g / m} 2 is desirable in the dry state.

<2.11 Sealing material (11)>
The sealing material 11 includes the weatherproof protective film 1, the ultraviolet cut film 2, the gas barrier film 3, the getter material film 4, the sealing material 5, the sealing material 7, the getter material film 8, the gas barrier film 9, and the back sheet 10. It is a member that seals the edge so that moisture and oxygen do not enter the space covered with these films.

The degree of moisture capacity required for the sealing member 11 is preferably water vapor transmission rate per day unit area (1 m ²⁾ is not more than ^{0.1g / m 2 / day, 0.05g} / m 2 / More preferably, it is not more than day. Conventionally, since it has been difficult to mount the sealing material 11 having such a high moisture-proof capability, it is possible to realize a solar cell including an excellent solar cell element such as a compound semiconductor solar cell element and an organic solar cell element. Although it was difficult, the implementation of the thin-film solar cell 14 utilizing the excellent properties of the compound semiconductor solar cell element and the organic solar cell element is facilitated by applying such a sealing material 11.

  Furthermore, since the thin film solar cell 14 is often heated by receiving light, it is preferable that the sealing material 11 also has heat resistance. From this viewpoint, the melting point of the constituent material of the sealing material 11 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 180 ° C. or lower. If the melting point is too low, the sealing material 11 may melt when the thin film solar cell 14 is used.

  Examples of the material constituting the sealing material 11 include polymers such as a fluorine resin, a silicone resin, and an acrylic resin. In addition, the sealing material 11 may be formed with 1 type of material, and may be formed with 2 or more types of materials. The sealing material 11 is provided at a position where at least the edges of the gas barrier films 3 and 9 can be sealed. Thereby, the space surrounded by at least the gas barrier films 3 and 9 and the sealing material 11 can be sealed, and moisture and oxygen can be prevented from entering the space.

  Although there is no restriction | limiting in the method of forming this sealing material 11, For example, it can form by inject | pouring material between the weather-resistant protective film 1 and the back sheet | seat 10. FIG. Specific examples of the forming method include the following methods. That is, for example, while the curing of the sealing material 5 proceeds, the semi-cured thin-film solar cell 14 is taken out from the laminating apparatus, and is the outer peripheral portion of the solar cell element 6, which is the weatherproof protective sheet 1 and the back sheet 10. A liquid polymer may be injected into a portion between the two and the polymer may be cured together with the sealing material 5. Further, after the sealing material 5 has been cured, it may be taken out from the laminating apparatus and cured alone. The temperature range for crosslinking and curing the polymer is usually 130 ° C. or higher, preferably 140 ° C. or higher, and is usually 180 ° C. or lower, preferably 170 ° C. or lower.

<2.12 Solar cell dimensions>
The thin film solar cell 14 of the present embodiment is usually a thin film member. By forming the thin film solar cell 14 as a film-like member in this way, the thin film solar cell 14 can be easily installed in building materials, automobiles, interiors, and 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.

<2.13 Solar Cell Manufacturing 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 performed reliably, and the sealing materials 5 and 7 from the end can be prevented from protruding and film thickness reduction due to overpressure can be suppressed, and dimensional stability can be ensured.

<2.14 Applications of solar cells>
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 films, vinyl chloride, polyethylene, cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene; paper materials such as paper and synthetic paper; metals such as stainless steel, titanium, and aluminum In addition, a composite material such as a material whose surface is coated or laminated in order to impart insulating properties may 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.

  When the example of the field | area which applies the thin film solar cell of this embodiment is given, the solar cell for building materials, the solar cell for motor vehicles, the solar cell for interiors, the solar cell for railways, the solar cell for ships, the solar cell for airplanes, for spacecraft It is suitable for use in solar cells, solar cells for home appliances, solar cells for mobile phones, solar cells for toys and the like. Specific examples include the following.

1. Building use 1.1 Solar cell as house roofing 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 of the house. Moreover, a roof tile can also be used directly as a base material. The solar cell of the present embodiment is suitable because it can be brought into close contact with the curve of the roof tile, taking advantage of the property that it has 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 embodiment has flexibility, it can be brought into close contact with a non-planar roof, for example, a folded roof. In this case, it is desirable to use a waterproof sheet in combination.

1.3 Top Light The thin film solar cell of the present embodiment can be used as an exterior at the entrance or at the atrium. An entrance or the like that has undergone some design processing often uses a curve, and in such a case, the flexibility of the thin-film solar cell of the present embodiment 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 a curtain wall. In addition, it can be attached to a spandrel or a vertical. In this case, although there is no restriction | limiting in the shape of a base material, Usually, a board | plate material is 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 Window 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 this embodiment is suitable for these applications.

2. Interior The thin film solar cell of this embodiment can also be attached to a blind slat. Since the thin film solar cell of this embodiment 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 use illumination light such as fluorescent lights is increasing, the current situation is that it is difficult to reduce the cultivation cost due to the electricity costs for lighting and replacement costs of light sources. Then, the thin film solar cell of this embodiment 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 in which an LED having a longer life than a fluorescent lamp and the solar cell of this embodiment is used, because the cost required for illumination can be reduced by about 30% compared to the current situation. Moreover, the solar cell of this embodiment 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 this embodiment can be used also for the outer wall of a parking lot, the sound insulation wall of an expressway, the outer wall of a water purification plant, etc.

5. Automobile The thin film solar cell of this embodiment can be used on the surfaces of automobile bonnets, roofs, trunk lids, doors, front fenders, rear fenders, pillars, bumpers, rearview mirrors, and the like. 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 used in the motor for driving, the battery for driving the motor, the electrical equipment and the battery for electrical equipment, the obtained electric power 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).

  EXAMPLES Hereinafter, although the Example of this invention is shown and this invention is demonstrated more concretely, this invention is not limited to a following example, unless it deviates from the summary.

ジヒドロメタノフラーレンＣ_６０（ＣＨ_２）（Ａ０）及びＣ_７０（ＣＨ_２）（Ａ９）は、以下のようにして合成した。 <Example 1: Synthesis of dihydromethanofullerene C ₆₀ (CH ₂ ) (A0) and C ₇₀ (CH ₂ ) (A9)>

Dihydro methanofullerene _{C 60 (CH 2) (A0} ) and _{C 70 (CH 2) (A9} ) was synthesized as follows.

公知文献Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，２００８，１３０（４６），１５４２９−１５４３６に従って、Ｃ_６０（ＣＨ_２ＳｉＭｅ_２Ｏ^ｉＰｒ）Ｈ（Ｅ２）を合成した。 <Synthesis Example 1-1>
[Synthesis of Intermediate E2]

Known literature J.A. Am. Chem. Soc. , 2008, 130 (46), 15429-15436, C ₆₀ (CH ₂ SiMe ₂ O ⁱ Pr) H (E2) was synthesized.

窒素雰囲気下、１００ｍＬ四口ナスフラスコに中間体Ｅ２（１１７ ｍｇ， ０．１３７ ｍｍｏｌ）およびｏ−ジクロロベンゼン（１０ ｍＬ）を入れ、減圧脱気後、窒素で復圧した。カリウムｔ−ブトキシドの１Ｍ ＴＨＦ溶液（Ａｌｄｒｉｃｈ製）（０．２１０ ｍＬ， ０．２１０ ｍｍｏｌ）を加え、約１０分間攪拌した。ヨウ素（３８ ｍｇ， ０．１５０ ｍｍｏｌ）を加え、さらに約２分間攪拌した。反応溶液をショートシリカゲルカラム（二硫化炭素）に供し、濃縮後、残渣を二硫化炭素−メタノールで再沈殿させた。ろ取し、減圧乾燥することにより、目的とするダイマー［Ｃ_６０（ＣＨ_２ＳｉＭｅ_２Ｏ^ｉＰｒ）］_２（Ｅ３）を、異性体混合物として、黒茶色固体として収率９９％（１１５ ｍｇ， ０．０６７５ ｍｍｏｌ， ＨＰＬＣ純度 ９９．７ ％）で得た。 [Synthesis of Intermediate E3]

Under a nitrogen atmosphere, intermediate E2 (117 mg, 0.137 mmol) and o-dichlorobenzene (10 mL) were placed in a 100 mL four-necked eggplant flask, and after degassing under reduced pressure, the pressure was restored with nitrogen. A 1M THF solution of potassium t-butoxide (manufactured by Aldrich) (0.210 mL, 0.210 mmol) was added, and the mixture was stirred for about 10 minutes. Iodine (38 mg, 0.150 mmol) was added and further stirred for about 2 minutes. The reaction solution was applied to a short silica gel column (carbon disulfide), and after concentration, the residue was reprecipitated with carbon disulfide-methanol. By filtration and drying under reduced pressure, the target dimer [C ₆₀ (CH ₂ SiMe ₂ O ⁱ Pr)] ₂ (E3) was obtained as a black-brown solid in a yield of 99% (115 mg, 115 mg, 0.0675 mmol, HPLC purity 99.7%).

窒素雰囲気下、二口ナスフラスコに塩化銅（ＩＩ）（１６．１ ｍｇ， ０．１２ ｍｍｏｌ， ６．０ ｅｑ）、中間体Ｅ３（３４．１ ｍｇ， ０．０２ ｍｍｏｌ）を加え、ｏ−ジクロロベンゼン（５ ｍＬ）に溶解させた。１００℃に加熱し、２時間攪拌後、室温に冷却した。メタノール（１ ｍＬ）を加えた後、トルエンで希釈し、シリカゲルろ過カラムに供した。ろ液を濃縮後、メタノールを加えて、沈殿物をろ取した。シリカゲルカラムクロマトグラフィー（二硫化炭素）に供することで、目的物であるジヒドロメタノフラーレンＣ_６０（ＣＨ_２）（化合物Ａ０）を収率９８％（２８．７ ｍｇ）で得た。 [Synthesis of Compound A0]

Under a nitrogen atmosphere, copper (II) chloride (16.1 mg, 0.12 mmol, 6.0 eq) and intermediate E3 (34.1 mg, 0.02 mmol) were added to a two-necked eggplant flask, and o- Dissolved in dichlorobenzene (5 mL). The mixture was heated to 100 ° C., stirred for 2 hours, and then cooled to room temperature. After adding methanol (1 mL), it was diluted with toluene and applied to a silica gel filtration column. The filtrate was concentrated, methanol was added, and the precipitate was collected by filtration. By subjecting it to silica gel column chromatography (carbon disulfide), dihydromethanofullerene C ₆₀ (CH ₂ ) (compound A0), which was the object, was obtained in a yield of 98% (28.7 mg).

Compound A0: ¹ H NMR (500 MHz, CDCl ₃ / CS ₂ ): δ 3.93 (s, 2H). APCI-MS (−) (m / z): calcd for OSiC ₇₀ H ₁₆ (M ⁻ ) 734.0157, found 734.02.

塩化（イソプロポキシ）ジメチルシリルメチルマグネシウム（（^ｉＰｒＯ）Ｍｅ_２ＳｉＣＨ_２ＭｇＣｌ）の代わりに、塩化ジメチルフェニルシリルメチルマグネシウム（Ｍｅ_２ＰｈＳｉＣＨ_２ＭｇＣｌ）を用いた以外は、合成例１−１における中間体Ｅ２の合成と同様にして、Ｃ_６０（ＣＨ_２ＳｉＭｅ_２Ｐｈ）Ｈ（Ｅ４）を合成した。 <Synthesis Example 1-2>
[Synthesis of Intermediate E4]

Intermediate in Synthesis Example 1-1, except that dimethylphenylsilylmethylmagnesium chloride (Me ₂ PhSiCH ₂ MgCl) was used instead of (isopropoxy) dimethylsilylmethylmagnesium chloride (( ⁱ PrO) Me ₂ SiCH ₂ MgCl) C ₆₀ (CH ₂ SiMe ₂ Ph) H (E4) was synthesized in the same manner as the synthesis of the body E2.

中間体Ｅ２の代わりに中間体Ｅ４を用いた以外は、合成例１−１における中間体Ｅ３の合成と同様にして、［Ｃ_６０（ＣＨ_２ＳｉＭｅ_２Ｐｈ）］_２（Ｅ５） [Synthesis of Intermediate E5]

[C ₆₀ (CH ₂ SiMe ₂ Ph)] ₂ (E5) In the same manner as in the synthesis of the intermediate E3 in Synthesis Example 1-1, except that the intermediate E4 was used instead of the intermediate E2.

窒素雰囲気下、二口ナスフラスコに塩化銅（ＩＩ）（１６．１ ｍｇ， ０．１２ ｍｍｏｌ， ６．０ ｅｑ）、中間体Ｅ５（３４．８ ｍｇ， ０．０２ ｍｍｏｌ）を加え、ｏ−ジクロロベンゼン（５ ｍＬ）に溶解させた。１００℃に加熱し、２時間攪拌後、室温に冷却した。メタノール（０．５ ｍＬ）を加えた後、トルエンで希釈し、シリカゲルろ過カラムに供した。ろ液を濃縮後、メタノールを加えて、沈殿物をろ取した。シリカゲルカラムクロマトグラフィー（二硫化炭素）に供することで、目的物であるジヒドロメタノフラーレンＣ_６０（ＣＨ_２）（Ａ０）を収率４６％で得た。 [Synthesis of Compound A0]

Under a nitrogen atmosphere, copper (II) chloride (16.1 mg, 0.12 mmol, 6.0 eq) and intermediate E5 (34.8 mg, 0.02 mmol) were added to a two-necked eggplant flask, and o- Dissolved in dichlorobenzene (5 mL). The mixture was heated to 100 ° C., stirred for 2 hours, and then cooled to room temperature. Methanol (0.5 mL) was added, diluted with toluene, and applied to a silica gel filtration column. The filtrate was concentrated, methanol was added, and the precipitate was collected by filtration. Dihydromethanofullerene C ₆₀ (CH ₂ ) (A0), which is the target product, was obtained in a yield of 46% by subjecting it to silica gel column chromatography (carbon disulfide).

<Synthesis Example 1-2a>
In Synthesis Example 1-2, copper (II) chloride was used when compound A0 was synthesized from intermediate E5. In Synthesis Example 1-2a, copper (II) triflate was used instead of copper (II) chloride. Otherwise, dihydromethanofullerene (A0) was synthesized by the same method as in Synthesis Example 1-2. In Synthesis Example 1-2a, the yield of compound A0 from intermediate E5 was 66%.

（イソプロポキシ）ジメチルシリルメチル塩化マグネシウム（（^ｉＰｒＯ）Ｍｅ_２ＳｉＣＨ_２ＭｇＣｌ）の代わりに、塩化トリメチルシリルメチルマグネシウム（Ｍｅ_３ＳｉＣＨ_２ＭｇＣｌ）を用いた以外は、合成例１−１における中間体Ｅ２の合成法と同様の方法で、Ｃ_６０（ＣＨ_２ＳｉＭｅ_３）Ｈ（Ｅ６）を合成した。 <Synthesis Example 1-3>
[Synthesis of Intermediate E6]

Intermediate E2 in Synthesis Example 1-1 except that trimethylsilylmethylmagnesium chloride (Me ₃ SiCH ₂ MgCl) was used instead of (isopropoxy) dimethylsilylmethyl magnesium chloride (( ⁱ PrO) Me ₂ SiCH ₂ MgCl) C ₆₀ (CH ₂ SiMe ₃ ) H (E6) was synthesized in the same manner as in the above synthesis method.

中間体Ｅ２の代わりに中間体Ｅ６を用いた以外は、合成例１−１における中間体Ｅ３の合成法と同様にして、［Ｃ_６０（ＣＨ_２ＳｉＭｅ_３）］_２（Ｅ７）を合成した。 [Synthesis of Intermediate E7]

[C ₆₀ (CH ₂ SiMe ₃ )] ₂ (E7) was synthesized in the same manner as in the synthesis of intermediate E3 in Synthesis Example 1-1 except that intermediate E6 was used instead of intermediate E2.

中間体Ｅ５の代わりに中間体Ｅ７を用いた以外は、合成例１−２における化合物Ａ０の合成法と同様にして、目的とするジヒドロメタノフラーレンＣ_６０（ＣＨ_２）（Ａ０）を収率９７％で得た。 [Synthesis of Compound A0]

The target dihydromethanofullerene C ₆₀ (CH ₂ ) (A0) was obtained in the same manner as in the synthesis method of Compound A0 in Synthesis Example 1-2 except that Intermediate E7 was used instead of Intermediate E5. %.

<Synthesis Example 1-4>
In Synthesis Example 1-4, dihydromethanofullerene (A0) was synthesized in one step from silylmethyl monoaddition fullerene (intermediates E2, E4, E6).

In Synthesis Example 1-4, the isolation yield when compound A0 is synthesized from each of intermediates E2, E4, and E6 is shown below. The synthesis method will be described in detail subsequently.

[Synthesis from Intermediate E2]
Synthesis Example 1 except that Intermediate E2 was used instead of Intermediate E3, and 1M THF solution (1.2 equivalents) of potassium t-butoxide was added and stirred for about 5 minutes before adding copper (II) chloride. The compound A0 was synthesized in the same manner as the method for synthesizing the compound A0 from the intermediate E3 described in 1.

[Synthesis from Intermediate E4]
Synthesis Example 1 except that Intermediate E4 was used instead of Intermediate E3, and 1M THF solution (1.2 equivalents) of potassium t-butoxide was added and stirred for about 5 minutes before adding copper (II) chloride. The compound A0 was synthesized in the same manner as the method for synthesizing the compound A0 from the intermediate E3 described in 1.

[Synthesis from Intermediate E6]
Synthetic Example 1 except that Intermediate E6 was used instead of Intermediate E3, and 1M THF solution (1.2 equivalents) of potassium t-butoxide was added and stirred for about 5 minutes before adding copper (II) chloride. The compound A0 was synthesized in the same manner as the method for synthesizing the compound A0 from the intermediate E3 described in 1.

窒素置換した５０ｍＬ二口フラスコ中に、マグネシウム（５８３ ｍｇ， ０．０２４ ｍｏｌ）を入れ、テトラヒドロフラン（５ ｍＬ）を添加した。ヨウ素（Ｉ_２）を少量加えた後、加熱還流した。ここに、（イソプロポキシジメチルシリル）クロロメタン（（^ｉＰｒＯ）Ｍｅ_２ＳｉＣＨ_２Ｃｌ， ３．５９ ｍＬ， ０．０２ ｍｏｌ）を徐々に滴下した後、テトラヒドロフラン（１４ ｍＬ）で希釈することで、塩化（イソプロポキシ）ジメチルシリルメチルマグネシウム（（^ｉＰｒＯ）Ｍｅ_２ＳｉＣＨ_２ＭｇＣｌ）のテトラヒドロフラン溶液（０．８７５ Ｍ）を調製した。別に、窒素置換した５００ｍＬ四口フラスコに、フラーレンＣ_７０（４６７ ｍｇ， ０．５５６ ｍｍｏｌ）、Ｎ，Ｎ−ジメチルホルムアミド（１．２９ ｍＬ， １６．６８ ｍｍｏｌ）、及び１，２−ジクロロベンゼン（１５０ ｍＬ）を加え、脱気した後、窒素で復圧した。ここに、上記のように調製した塩化（イソプロポキシ）ジメチルシリルメチルマグネシウム（（^ｉＰｒＯ）Ｍｅ_２ＳｉＣＨ_２ＭｇＣｌ）のテトラヒドロフラン溶液（０．８７５ Ｍ）のうち１．９１ｍＬ（１．６６８ ｍｍｏｌ， ３当量）をシリンジで加え、５分間攪拌した後、脱気した飽和塩化アンモニウム水溶液を０．９ｍＬ加えて、室温で攪拌した。得られた溶液を濃縮後、二硫化炭素で希釈し、二硫化炭素：ヘキサン＝１：１〜１：０の混合溶媒を展開溶媒としてシリカゲルカラムクロマトグラフィー精製を行うことにより、目的物であるＣ_７０（ＣＨ_２ＳｉＭｅ_２Ｏ^ｉＰｒ）Ｈ（中間体Ｅ８）の異性体混合物を収率５８％（３１３ ｍｇ， ０．３２２ ｍｍｏｌ）で黒色固体として得た。 <Synthesis Example 1-5>
[Synthesis of Intermediate E8]

Magnesium (583 mg, 0.024 mol) was placed in a nitrogen-substituted 50 mL two-necked flask, and tetrahydrofuran (5 mL) was added. A small amount of iodine (I ₂ ) was added, and the mixture was heated to reflux. Here, by dilution with (isopropoxycarbonyl butyldimethylsilyl) chloromethane ^{_{((i PrO) Me 2 SiCH}} 2 Cl, 3.59 mL, 0.02 mol) was slowly added dropwise, tetrahydrofuran (14 mL), A tetrahydrofuran solution (0.875 M) of (isopropoxy) dimethylsilylmethylmagnesium chloride (( ⁱ PrO) Me ₂ SiCH ₂ MgCl) was prepared. Separately, in a nitrogen-substituted 500 mL four-necked flask, fullerene C ₇₀ (467 mg, 0.556 mmol), N, N-dimethylformamide (1.29 mL, 16.68 mmol), and 1,2-dichlorobenzene ( 150 mL) was added, degassed, and then re-pressured with nitrogen. Here, prepared chloride (isopropoxy) dimethylsilylmethyl magnesium as described above 1.91mL of tetrahydrofuran ^{_{((i PrO) Me 2 SiCH}} 2 MgCl) (0.875 M) (1.668 mmol, 3 Equivalent) was added with a syringe and stirred for 5 minutes, and then 0.9 mL of a degassed saturated aqueous ammonium chloride solution was added and stirred at room temperature. The obtained solution is concentrated, diluted with carbon disulfide, and purified by silica gel column chromatography using a mixed solvent of carbon disulfide: hexane = 1: 1 to 1: 0 as a developing solvent. An isomer mixture of ₇₀ (CH ₂ SiMe ₂ O ⁱ Pr) H (intermediate E8) was obtained as a black solid in 58% yield (313 mg, 0.322 mmol).

窒素雰囲気下、２００ｍＬ三口ナスフラスコに中間体Ｅ８（３９９ ｍｇ， ０．４１０ ｍｍｏｌ）及びｏ−ジクロロベンゼン（３０ ｍＬ）を入れ、減圧脱気後、窒素で復圧した。カリウムｔ−ブトキシドの１Ｍテトラヒドロフラン溶液（Ａｌｄｒｉｃｈ製）（０．６２７ ｍＬ， ０．６２７ ｍｍｏｌ）を加え、約１０分間攪拌した。その後ヨウ素（１１４ ｍｇ， ０．４４７ ｍｍｏｌ）を加え、さらに約２分間攪拌した。反応溶液をショートシリカゲルカラム（トルエン）に供し、濃縮後、残渣にメタノールを加え、沈殿物をろ取して減圧乾燥することにより、目的とするダイマー［Ｃ_７０（ＣＨ_２ＳｉＭｅ_２Ｏ^ｉＰｒ）］_２（中間体Ｅ９）の粗生成物（４３０ ｍｇ）を得た。 [Synthesis of Intermediate E9]

Under a nitrogen atmosphere, Intermediate E8 (399 mg, 0.410 mmol) and o-dichlorobenzene (30 mL) were placed in a 200 mL three-necked eggplant flask, and after degassing under reduced pressure, the pressure was restored with nitrogen. A 1M tetrahydrofuran solution (manufactured by Aldrich) of potassium t-butoxide (0.627 mL, 0.627 mmol) was added, and the mixture was stirred for about 10 minutes. Thereafter, iodine (114 mg, 0.447 mmol) was added, and the mixture was further stirred for about 2 minutes. The reaction solution was applied to a short silica gel column (toluene), concentrated, methanol was added to the residue, the precipitate was collected by filtration and dried under reduced pressure to obtain the target dimer [C ₇₀ (CH ₂ SiMe ₂ O ⁱ Pr). ] ₂ (Intermediate E9) crude product (430 mg) was obtained.

窒素雰囲気下、二口ナスフラスコに塩化銅（ＩＩ）（１．１８ ｇ， ８．８０ ｍｍｏｌ， ６．０ ｅｑ）及び上記のように合成した中間体Ｅ９の粗生成物（２．８５ ｇ， ＜１．４６６ ｍｍｏｌ）を加え、ｏ−ジクロロベンゼン（２００ ｍＬ）に溶解させた。１００℃に加熱し、６時間攪拌後、室温に冷却した。メタノール（４００ ｍＬ）を加え、沈殿物をろ取した。シリカゲルカラムクロマトグラフィー（二硫化炭素）に供することで、ジヒドロメタノフラーレンＣ_７０（ＣＨ_２）（化合物Ａ９）を異性体混合物として収率８０％（２．００ ｇ， ２．３４ ｍｍｏｌ）で得た。 [Synthesis of Compound A9]

Under a nitrogen atmosphere, in a two-necked eggplant flask, copper (II) chloride (1.18 g, 8.80 mmol, 6.0 eq) and a crude product of intermediate E9 synthesized as described above (2.85 g, <1.466 mmol) was added and dissolved in o-dichlorobenzene (200 mL). The mixture was heated to 100 ° C., stirred for 6 hours, and then cooled to room temperature. Methanol (400 mL) was added and the precipitate was collected by filtration. Dihydromethanofullerene C ₇₀ (CH ₂ ) (compound A9) was obtained as an isomer mixture in a yield of 80% (2.00 g, 2.34 mmol) by subjecting it to silica gel column chromatography (carbon disulfide). .

Compound A9: ¹ H NMR (400 MHz, CDCl ₃ / CS ₂ ): δ 2.85 (s, 2H), 2.80 (d, 1H, J = 6.0 Hz), 2.54 (d, 1H , J = 6.0 Hz).

<Example 2: Synthesis of various methanofullerene compounds>
In Synthesis Example 2, various methanofullerene compounds are synthesized using dihydromethanofullerene (A0).

窒素雰囲気下、３００ｍＬ四口ナスフラスコ中、化合物Ａ０（３００ ｍｇ， ０．４０９ ｍｍｏｌ）、インデン（１．１４ ｍＬ、９．８１ ｍｍｏｌ）をｏ−ジクロロペンゼン（１４０ ｍＬ）に加え、減圧脱気後、再び窒素雰囲気下に戻し、加熱還流した。１０時間後、インデン（１．７２ ｍＬ， １４．７ ｍｍｏｌ） を追加し、さらに１０時間加熱還流した。室温に戻し、溶媒を減圧留去した後、シリカゲルカラムクロマトグラフィー（二硫化炭素：ヘキサン＝１：２〜１：０）に供した後、ＧＰＣ精製（クロロホルム）を行うことにより、Ｃ_６０（ＣＨ_２）（Ｉｎｄ）（Ａ１）を収率４７％（１６４ ｍｇ， ０．１９３ ｍｍｏｌ）、Ｃ_６０（ＣＨ_２）（Ｉｎｄ）_２（Ａ２）を収率１７％（６７ ｍｇ， ０．０６９ ｍｍｏｌ）でそれぞれ位置異性体の混合物として得た。それぞれについて、質量分析（ＡＰＣＩ法， ｎｅｇａｔｉｖｅ）により、目的物の質量と一致するｍ／ｚ：８５０［Ｍ⁻］、ｍ／ｚ：９６６［Ｍ⁻］を検出した。 <Synthesis Example 2-1: Synthesis of methanofullerene compounds A1 and A2>

Under a nitrogen atmosphere, compound A0 (300 mg, 0.409 mmol) and indene (1.14 mL, 9.81 mmol) were added to o-dichlorobenzene (140 mL) in a 300 mL four-necked eggplant flask and depressurized. After that, the atmosphere was again returned to a nitrogen atmosphere and heated to reflux. After 10 hours, indene (1.72 mL, 14.7 mmol) was added, and the mixture was further heated to reflux for 10 hours. After returning to room temperature and distilling off the solvent under reduced pressure, the residue was subjected to silica gel column chromatography (carbon disulfide: hexane = 1: 2 to 1: 0) and then subjected to GPC purification (chloroform), whereby C ₆₀ (CH ₂ ) (Ind) (A1) in 47% yield (164 mg, 0.193 mmol), C ₆₀ (CH ₂ ) (Ind) ₂ (A2) in 17% yield (67 mg, 0.069 mmol) To obtain a mixture of regioisomers. About each, m / z: 850 [M < ^- >] and m / z: 966 [M < ^- >] which correspond to the mass of a target object were detected by mass spectrometry (APCI method, negative).

窒素雰囲気下、３００ｍＬ三口ナスフラスコ中、化合物Ａ０（３００ ｍｇ， ０．４０９ ｍｍｏｌ）、ヨウ化テトラｎ−ブチルアンモニウム（ＴＢＡＩ： ６０４ ｍｇ， １．６３ ｍｍｏｌ）、トルエン（１４０ ｍＬ）を入れた。減圧脱気後、再び窒素雰囲気下に戻し、α、α’−ジブロモ−ｏ−キシレン（４３２ ｍｇ， １．６３ ｍｍｏｌ）を加えて加熱還流した。１０時間後、ヨウ化テトラｎ−ブチルアンモニウム（ＴＢＡＩ： ９０６ ｍｇ， ２．４５ ｍｍｏｌ）、α，α’−ジブロモ−ｏ−キシレン（６４７ ｍｇ， ２．４５ ｍｍｏｌ）を追加し、さらに約６時間加熱還流した。室温に戻し、シリカゲルろ過カラム（トルエン）に供し、濃縮した。シリカゲルカラムクロマトグラフィー（二硫化炭素）に供した後、ＧＰＣ精製（クロロホルム）を行うことにより、目的とするＣ_６０（ＣＨ_２）（ＱＭ）（Ａ３）を収率１３％（４３ ｍｇ， ０．０５１３ ｍｍｏｌ）で、Ｃ_６０（ＣＨ_２）（ＱＭ）_２（Ａ４）を収率３０％（１１７ ｍｇ， ０．１２４ ｍｍｏｌ）でそれぞれ位置異性体の混合物として得た。質量分析（ＡＰＣＩ法， ｎｅｇａｔｉｖｅ）により、目的物の質量と一致するｍ／ｚ：８３８［Ｍ⁻］、ｍ／ｚ：９４２［Ｍ⁻］をそれぞれ検出した。 <Synthesis Example 2-2: Synthesis of methanofullerene compounds A3 and A4>

Under a nitrogen atmosphere, Compound A0 (300 mg, 0.409 mmol), tetra n-butylammonium iodide (TBAI: 604 mg, 1.63 mmol), and toluene (140 mL) were placed in a 300 mL three-necked eggplant flask. After degassing under reduced pressure, the atmosphere was returned to a nitrogen atmosphere again, α, α′-dibromo-o-xylene (432 mg, 1.63 mmol) was added, and the mixture was heated to reflux. After 10 hours, tetra-n-butylammonium iodide (TBAI: 906 mg, 2.45 mmol) and α, α′-dibromo-o-xylene (647 mg, 2.45 mmol) were added, and about 6 hours further. Heated to reflux. It returned to room temperature, it used for the silica gel filtration column (toluene), and concentrated. After subjecting to silica gel column chromatography (carbon disulfide), GPC purification (chloroform) was performed to obtain the target C ₆₀ (CH ₂ ) (QM) (A3) in a yield of 13% (43 mg, 0. 3). 0513 mmol), C ₆₀ (CH ₂ ) (QM) ₂ (A4) was obtained as a mixture of regioisomers in 30% yield (117 mg, 0.124 mmol), respectively. By mass spectrometry (APCI method, negative), m / z: 838 [M ⁻ ] and m / z: 942 [M ⁻ ] corresponding to the mass of the target product were detected.

窒素雰囲気下、１００ｍＬ四口ナスフラスコに、化合物Ａ０（２００ ｍｇ， ０．２７２ ｍｍｏｌ）、ＭＢＢＴ（Ｊ．Ｏｒｇ．Ｃｈｅｍ．１９９５，６０，５３２−５３８に従って合成したものを使用した）（１１２ ｍｇ， ０．２９９ ｍｍｏｌ）、ｏ−ジクロロベンゼン（１０ ｍＬ）を加えた。減圧脱気後、再び窒素雰囲気下に戻し、８０℃に加熱後、ナトリウムメトキシド（１６．２ ｍｇ， ０．３００ ｍｍｏｌ）を加え、約４時間攪拌した。ナトリウムメトキシド（５．８ ｍｇ）を追加し、さらに約４時間攪拌した。ＭＢＢＴ（１１２ ｍｇ）、ナトリウムメトキシド（１６．２ ｍｇ）を追加し、さらに約９時間攪拌した。室温まで放冷し、シリカゲルろ過カラム（ｏ−ジクロロベンゼン（５０ ｍＬ）−酢酸エチル（５０ ｍＬ））に供した。酢酸エチルを減圧で留去し、残ったｏ−ジクロロベンゼン溶液を３００ｍＬ四口ナスフラスコ中に移し、減圧脱気後、再び窒素雰囲気下に戻し、約７時間加熱還流した。溶媒を減圧留去した後、シリカゲルカラムクロマトグラフィー（トルエン−酢酸エチル）に供することで、目的とするＣ_６０（ＣＨ_２）（ＰＣＢＭ）（Ａ５）を収率２５％（６２ ｍｇ， ０．０６７ ｍｍｏｌ）で位置異性体の混合物として得た。質量分析（ＡＰＣＩ法， ｎｅｇａｔｉｖｅ）により、目的物の質量と一致するｍ／ｚ：９２４［Ｍ⁻］を検出した。 <Synthesis Example 2-3: Synthesis of methanofullerene compound A5>

In a 100 mL four-necked eggplant flask under a nitrogen atmosphere, compound A0 (200 mg, 0.272 mmol), MBBT (synthesized according to J. Org. Chem. 1995, 60, 532-538) (112 mg, 0.299 mmol), o-dichlorobenzene (10 mL) was added. After degassing under reduced pressure, the atmosphere was returned to a nitrogen atmosphere again, heated to 80 ° C., sodium methoxide (16.2 mg, 0.300 mmol) was added, and the mixture was stirred for about 4 hours. Sodium methoxide (5.8 mg) was added, and the mixture was further stirred for about 4 hours. MBBT (112 mg) and sodium methoxide (16.2 mg) were added, and the mixture was further stirred for about 9 hours. The mixture was allowed to cool to room temperature and applied to a silica gel filtration column (o-dichlorobenzene (50 mL) -ethyl acetate (50 mL)). Ethyl acetate was distilled off under reduced pressure, and the remaining o-dichlorobenzene solution was transferred into a 300 mL four-necked eggplant flask, degassed under reduced pressure, then returned to a nitrogen atmosphere, and heated to reflux for about 7 hours. After the solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography (toluene-ethyl acetate) to obtain the intended C ₆₀ (CH ₂ ) (PCBM) (A5) in a yield of 25% (62 mg, 0.067). mmol)) as a mixture of regioisomers. By mass spectrometry (APCI method, negative), m / z: 924 [M ⁻ ] corresponding to the mass of the target product was detected.

窒素雰囲気下、３００ｍＬ四口ナスフラスコ中、化合物Ａ９（４００ ｍｇ， ０．４６８ ｍｍｏｌ）及びインデン（２．７３ ｍＬ， ２３．４ ｍｍｏｌ）をｏ−ジクロロペンゼン（１８０ ｍＬ）に加え、減圧脱気後、再び窒素雰囲気下に戻し、加熱還流した。１０時間後、インデン（１．３７ ｍＬ， １１．７ ｍｍｏｌ）を追加し、さらに１０時間加熱還流した。室温に戻し、溶媒を減圧留去して、シリカゲルカラムクロマトグラフィー（二硫化炭素：ヘキサン＝２：１〜１：０）に供した後、ＧＰＣ精製（クロロホルム）を行うことにより、Ｃ_７０（ＣＨ_２）（Ｉｎｄ）（化合物Ａ１０）を収率３６％（１６４ ｍｇ， ０．１６９ ｍｍｏｌ）で、Ｃ_７０（ＣＨ_２）（Ｉｎｄ）_２（化合物Ａ１１）を収率４％（１８．２ ｍｇ， ０．０１６８ ｍｍｏｌ）で、それぞれ位置異性体の混合物として得た。質量分析（ＡＰＣＩ法， ｎｅｇａｔｉｖｅ）により、化合物Ａ１０と化合物Ａ１１のそれぞれについて、目的物の質量と一致するｍ／ｚ：９７０［Ｍ⁻］及びｍ／ｚ：１０８６［Ｍ⁻］を検出した。 <Synthesis Example 2-4: Synthesis of methanofullerene compounds A10 and A11>

Under a nitrogen atmosphere, compound A9 (400 mg, 0.468 mmol) and indene (2.73 mL, 23.4 mmol) were added to o-dichlorobenzene (180 mL) in a 300 mL four-necked eggplant flask and depressurized. After that, the atmosphere was again returned to a nitrogen atmosphere and heated to reflux. After 10 hours, indene (1.37 mL, 11.7 mmol) was added, and the mixture was further heated to reflux for 10 hours. After returning to room temperature, the solvent was distilled off under reduced pressure and subjected to silica gel column chromatography (carbon disulfide: hexane = 2: 1 to 1: 0), followed by GPC purification (chloroform) to obtain C ₇₀ (CH ₂₎ (Ind) (compound A10) 36% yield (164 mg, with _{0.169 mmol), C 70 (CH} 2) (Ind) 2 ( compound A11) 4% yield (18.2 mg, 0.0168 mmol) in each case as a mixture of regioisomers. By mass spectrometry (APCI method, negative), m / z: 970 [M ⁻ ] and m / z: 1086 [M ⁻ ] corresponding to the mass of the target product were detected for each of Compound A10 and Compound A11.

<Example 3>
In Synthesis Example 3, various methanofullerene compounds are synthesized by other methods instead of adding an additional group to dihydromethanofullerene (A0). Specifically, a method of cleaving a fullerene dimer having an addition group (Synthesis Examples 3-1 and 3-2), and a dihydromethano group by allowing an oxidant to act on the silylmethyl addition fullerene having an addition group A method of introducing the will be described.

<Synthesis Example 3-1: Synthesis of methanofullerene compound A6>

中間体Ｆ１は、塩化（イソプロポキシ）ジメチルシリルメチルマグネシウム（（^ｉＰｒＯ）Ｍｅ_２ＳｉＣＨ_２ＭｇＣｌ）の代わりに、塩化ジメチルヘキシルシリルメチルマグネシウム（Ｃ_６Ｈ_１３Ｍｅ_２ＳｉＣＨ_２ＭｇＣｌ）を用いた以外は、合成例１−１における中間体Ｅ２の合成法と同様にして合成した。 [Synthesis of Intermediate F1]

Intermediate F1 was obtained by using dimethylhexylsilylmethylmagnesium chloride (C ₆ H ₁₃ Me ₂ SiCH ₂ MgCl) in place of (isopropoxy) dimethylsilylmethylmagnesium chloride (( ⁱ PrO) Me ₂ SiCH ₂ MgCl) Was synthesized in the same manner as in the synthesis method of Intermediate E2 in Synthesis Example 1-1.

中間体Ｆ２は、中間体Ｅ２の代わりに中間体Ｆ１を用いた以外は、合成例１−１における中間体Ｅ３の合成法と同様にして合成した。 [Synthesis of Intermediate F2]

The intermediate F2 was synthesized in the same manner as the synthesis method of the intermediate E3 in Synthesis Example 1-1 except that the intermediate F1 was used instead of the intermediate E2.

中間体Ｆ２を用いて以下の反応を行うことにより、中間体Ｆ３を合成した。中間体Ｆ３の合成は、以下の方法（１）（２）のどちらを用いても行うことができた。 [Synthesis of Intermediate F3]

Intermediate F3 was synthesized by carrying out the following reaction using intermediate F2. The synthesis of intermediate F3 could be performed using either of the following methods (1) and (2).

[Synthesis of Intermediate F3 (1)]
Under a nitrogen atmosphere, put intermediate F2 (600 mg, purity 83%, contining C ₆₀ 10%, 0.284 mmol), PhC≡CCOOEt (560 μl, 3.40 mmol) in a two-necked flask, and o- Dissolved in dichlorobenzene (30 mL). Heated at 140 ° C. for 8 hours. Methanol was added, the solid was collected by filtration, and subjected to silica gel column chromatography (carbon disulfide), whereby Intermediate F3 was obtained as a mixture of dimers and a yield of 37% (205 mg, purity 99%) was obtained.

[Synthesis of Intermediate F3 (2)]
Under a nitrogen atmosphere, Intermediate F2 (500 mg, purity 99%, 0.285 mmol) and PhC≡CCOOEt (470 μL, 2.85 mmol) were placed in a two-necked flask, and o-dichlorobenzene (30 mL). Dissolved in. Heated at 160 ° C. for 2.5 hours. Methanol was added, and the solid was collected by filtration and subjected to silica gel column chromatography (carbon disulfide) to obtain Intermediate F3 as a mixture of dimers in a yield of 37% (203 mg, purity 96%).

窒素雰囲気下、二口フラスコ中に、中間体Ｆ３（８６ ｍｇ， ０．６３９ ｍｍｏｌ）を入れ、ｏ−ジクロロベンゼン（１１ ｍＬ）を加えた。１４０℃で４時間加熱した。メタノールを加え、固体をろ取し、シリカゲルカラムクロマトグラフィー（二硫化炭素）に供した。先に溶出したバンドを集めることで、ジヒドロメタノフラーレン（Ａ０）（７３ ｍｇ， ｙｉｅｌｄ ９４ ％）を得た。次に溶出したバンドを集めることで、化合物Ａ６（９３ ｍｇ， ｙｉｅｌｄ ９６ ％， ｐｕｒｉｔｙ ９８ ％）を得た。 [Synthesis of Compound A6]

Under a nitrogen atmosphere, Intermediate F3 (86 mg, 0.639 mmol) was placed in a two-necked flask, and o-dichlorobenzene (11 mL) was added. Heated at 140 ° C. for 4 hours. Methanol was added, and the solid was collected by filtration and subjected to silica gel column chromatography (carbon disulfide). The previously eluted band was collected to obtain dihydromethanofullerene (A0) (73 mg, yield 94%). Next, the eluted band was collected to obtain Compound A6 (93 mg, yield 96%, purity 98%).

<Synthesis Example 3-2: Synthesis of methanofullerene compound A7>

合成例１−１で説明した中間体Ｅ３（１ ｇ， ｐｕｒｉｔｙ ９５ ％， ０．５５８ ｍｍｏｌ）、２−ＭｅＯＣ_６Ｈ_４Ｃ≡ＣＣ_６Ｈ_１３（１．２７ ｇ， １．３５ ｍＬ， ５．８８ ｍｍｏｌ）を入れ、ｏ−ジクロロベンゼン（５０ ｍＬ）に溶解させた。１６０℃で２．５時間加熱した。メタノールを加え、固体をろ取し、シリカゲルカラムクロマトグラフィー（二硫化炭素：トルエン＝２０：１）に供することで、中間体Ｆ４をダイマーの混合物として収率６７％（７５０ ｍｇ， ｐｕｒｉｔｙ ６０ ％）で得た。 [Synthesis of Intermediate F4]

Intermediate E3 described in Synthesis Example 1-1 (1 g, purity 95%, 0.558 mmol), 2-MeOC ₆ H ₄ C≡CC ₆ H ₁₃ (1.27 g, 1.35 mL, 5. 88 mmol) was added and dissolved in o-dichlorobenzene (50 mL). Heated at 160 ° C. for 2.5 hours. Methanol was added, the solid was collected by filtration, and subjected to silica gel column chromatography (carbon disulfide: toluene = 20: 1) to give intermediate F4 as a dimer mixture in a yield of 67% (750 mg, purity 60%). Got in.

窒素雰囲気下、二口フラスコ中に、中間体Ｆ４（７５０ ｍｇ， ｐｕｒｉｔｙ ６０ ％， ０．２３５ ｍｍｏｌ）、ＣｕＣｌ_２（８６ ｍｇ， １．８７４ ｍｍｏｌ）を入れ、ｏ−ジクロロベンゼン（３０ ｍＬ）を加えた。１４０℃で４時間加熱した。メタノールを加え、固体をろ取し、シリカゲルカラムクロマトグラフィー（二硫化炭素：ヘキサン＝１：２）に供した。先に溶出したバンドを集めることで、ジヒドロメタノフラーレン（Ａ０）（１５２ ｍｇ， ｙｉｅｌｄ ８８ ％）を得た。次に溶出したバンドを集めることで、化合物Ａ７（１８０ ｍｇ， ｙｉｅｌｄ ８１％， ｐｕｒｉｔｙ ９９％）を得た。 [Synthesis of Compound A7]

Under a nitrogen atmosphere, in a two-necked flask, intermediate F4 (750 mg, purity 60%, 0.235 mmol), CuCl ₂ (86 mg, 1.874 mmol) were placed, and o-dichlorobenzene (30 mL) was added. added. Heated at 140 ° C. for 4 hours. Methanol was added, and the solid was collected by filtration and subjected to silica gel column chromatography (carbon disulfide: hexane = 1: 2). The previously eluted band was collected to obtain dihydromethanofullerene (A0) (152 mg, yield 88%). Next, the eluted band was collected to obtain Compound A7 (180 mg, yield 81%, purity 99%).

<Synthesis Example 3-3: Synthesis of methanofullerene compound A8>

二口フラスコ中、化合物Ｆ５（Ｃ_６０（ＣＨ_２Ｐｈ）_２）（２００ ｍｇ， ０．２２ ｍｍｏｌ）、ＴＨＦ（５０ ｍＬ）を入れ、脱気後、窒素雰囲気下、室温で攪拌した。化合物Ｆ５は、周知の方法によって、例えばＪ．Ｏｒｇ．Ｃｈｅｍ．２００７，７２，２５３８−２５４２．に従って合成できる。ここに、^ｉＰｒＯＭｅ_２ＳｉＣＨ_２ＭｇＣｌのＴＨＦ溶液（０．９７ ｍＬ， ０．７３ Ｍ， ０．７１ ｍｍｏｌ）を加え、２時間２０分間攪拌した後、飽和塩化アンモニウム水溶液（０．１ ｍＬ）を加え反応をクエンチした。溶媒を減圧留去し、シリカゲルカラムクロマトグラフィー（二硫化炭素：トルエン＝１：０〜１：１）に供することで、中間体Ｆ６を茶色固体として１６５ｍｇ（７２％ ｙｉｅｌｄ）得た。中間体Ｆ６は保存中に分解しやすい為、そのまますぐに次の反応に用いた。 [Synthesis of Intermediate F6]

In a two-necked flask, compound F5 (C ₆₀ (CH ₂ Ph) ₂ ) (200 mg, 0.22 mmol) and THF (50 mL) were added, and after deaeration, the mixture was stirred at room temperature under a nitrogen atmosphere. Compound F5 can be prepared by well-known methods, for example, J. Org. Org. Chem. 2007, 72, 2538-2542. Can be synthesized according to To this was added ⁱ PrOMe ₂ SiCH ₂ MgCl in THF (0.97 mL, 0.73 M, 0.71 mmol), and the mixture was stirred for 2 hours and 20 minutes, and then saturated aqueous ammonium chloride solution (0.1 mL) was added. The reaction was quenched. The solvent was distilled off under reduced pressure and subjected to silica gel column chromatography (carbon disulfide: toluene = 1: 0 to 1: 1) to obtain 165 mg (72% yield) of intermediate F6 as a brown solid. Since intermediate F6 was easily decomposed during storage, it was immediately used in the next reaction as it was.

_{C 60 (CH 2 Ph) 2} (CH 2 SiMe 2 O i Pr) H (F6): APCI-HRMS (-): m / z calcd. for C ₈₀ H ₃₀ OSi (M−H ⁺ ), 1033.1993; found, 10331.968.

中間体Ｆ６（８９ ｍｇ， ０．０９０ ｍｍｏｌ）と臭化銅（ＩＩ）（１２０ ｍｇ， ０．５４ ｍｍｏｌ）のｏ−ジクロロベンゼン（２０ ｍＬ）懸濁液に対して、カリウムｔ−ブトキシドの１Ｍ ＴＨＦ溶液（９９ μｌ， ０．０９９ ｍｍｏｌ）を加えた。室温で５分間攪拌後、反応溶液を１２０℃で５時間加熱した。溶媒を減圧留去した後、シリカゲルカラムクロマトグラフィー（二硫化炭素：ヘキサン＝１：４〜１：２）に供することで、化合物Ａ８（４６ ｍｇ， ５６ ％ ｙｉｅｌｄ）を得た。 [Synthesis of Compound A8]

1M potassium t-butoxide against a suspension of intermediate F6 (89 mg, 0.090 mmol) and copper (II) bromide (120 mg, 0.54 mmol) in o-dichlorobenzene (20 mL) A THF solution (99 μl, 0.099 mmol) was added. After stirring at room temperature for 5 minutes, the reaction solution was heated at 120 ° C. for 5 hours. After the solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography (carbon disulfide: hexane = 1: 4 to 1: 2) to obtain Compound A8 (46 mg, 56% yield).

(C ₆₀ (CH ₂ ) (CH ₂ Ph) ₂ ) (A8): ¹ H NMR (500 MHz, CDCl ₃ ): 2.88 (1H, J _AB = 6.5 Hz), 3.24 (1H, J _AB = 6.0 Hz), 3.58 (2H, s, C ₆ H ₄ CH ₂ ), 3.64 (2H, d, J _AB = 13.2 Hz, C ₆ H ₄ CH ₂ ), 3 _{.71 (2H, d, J AB} = 13.8 Hz, C 6 H 4 CH 2), 7.22 (1H, d, J = 8 Hz, C 6 H 4), 7.32 (1H, m, C ₆ H ₄ ), 7.42 (3H, m, C ₆ H ₄ ), 7.52 (6H, m, C ₆ H ₄ ); ¹³ C NMR (125 MHz, CDCl ₃ ): δ 31.02 ( _{1C, methano- C H 2),} 47.57 (1C, Ar C H 2), _{9.40 (1C, Ar C H 2} ), 57.71 (1C, C 60 sp 3 - C), 58.50 (1C, C 60 sp 3 - C), 62.22 (1C, C 60 sp 3 _{- C), 64.97 (1C,} C 60 sp 3 - C), 127.31, 127.85, 128.36, 128.85, 131.05, 131.12, 140.95, 141.82, 141.94, 142.43, 142.49, 142.56, 142.94, 143.08, 143.60, 143.75, 143.88, 143.95, 144.01, 144.12, 144. 24, 144.27, 144.38, 144.44, 144.54, 144.88, 145.42, 145.50, 145.60, 145.88, 145.97, 146.09, 146.13, 146.15, 146.23, 146.41, 146.54, 146.76, 146.86, 146.94, 147.36, 147.42, 147.60, 148. 51, 149.01, 149.21, 149.37, 150.69, 152.07, 152.10, 152.60, 152.78, 153.02, 153.50, 154.94; APCI-HRMS ( -): M / z calcd. for C ₇₅ H ₁₆ (M ⁻ ), 916.1252; found, 916.1275

<Comparative Example 4>
In this comparative example, various fullerene compounds are synthesized as comparative examples for comparing physical properties with the methanofullerene compound synthesized as described above.

Ｃ_６０（Ｉｎｄ）（Ｇ１）及びＣ_６０（Ｉｎｄ）_２（Ｇ２）の合成は、特許文献（国際公開第２００８／０１８９３１号）を参考にして行った。化合物Ｇ２は、ＧＰＣで分取精製することにより、ビス付加体の位置異性体混合物として取得した。質量分析（ＡＰＣＩ法， ｎｅｇａｔｉｖｅ）により、化合物Ｇ２の質量と一致するｍ／ｚ： ９５２［Ｍ⁻］を検出した。分解開始温度は２７０℃であった。ガラス転移温度は、２００℃以下で観測されなかった。化合物Ｇ２の合成過程では化合物Ｇ１も副生するため、これを単離することによりＣ_６０（Ｉｎｄ）（Ｇ１）も得ることができた。 [Comparative Example 4-1: Synthesis of Compounds G1 and G2]

The synthesis of C ₆₀ (Ind) (G1) and C ₆₀ (Ind) ₂ (G2) was performed with reference to a patent document (International Publication No. 2008/018931). Compound G2 was obtained as a regioisomer mixture of bis-adducts by preparative purification using GPC. By mass spectrometry (APCI method, negative), m / z: 952 [M ⁻ ] corresponding to the mass of the compound G2 was detected. The decomposition start temperature was 270 ° C. The glass transition temperature was not observed below 200 ° C. Since compound G1 is also produced as a by-product in the process of synthesizing compound G2, C ₆₀ (Ind) (G1) could also be obtained by isolating it.

窒素雰囲気下、５００ｍＬ三口ナスフラスコ中、フラーレンＣ_６０ （５００ ｍｇ， ０．６９４ ｍｍｏｌ）、ヨウ化テトラｎ−ブチルアンモニウム（ＴＢＡＩ： １．２８ｇ， ３．４７ｍｍｏｌ， ５ ｅｑ．）、トルエン（２３０ ｍＬ）を入れた。減圧脱気後、再び窒素雰囲気下に戻し、α、α’−ジブロモ−ｏ−キシレン（９１６ ｍｇ， ３．４７ ｍｍｏｌ， ５ ｅｑ．）を加えて加熱還流した。１０時間後、室温に戻し、シリカゲルろ過カラム（トルエン）に供し、濃縮した。シリカゲルカラムクロマトグラフィー（二硫化炭素：ヘキサン＝１：２）に供した後、ＧＰＣ精製（クロロホルム）を行うことにより、収率４７％（３０４ ｍｇ， ０．３２８ ｍｍｏｌ）で位置異性体混合物としてＣ_６０（ＱＭ）_２（Ｇ４）を得た。質量分析（ＡＰＣＩ法， ｎｅｇａｔｉｖｅ）により、目的物の質量と一致するｍ／ｚ： ９２８［Ｍ⁻］を検出した。化合物Ｇ４の合成過程では化合物Ｇ３も副生するため、これを単離することによりＣ_６０（ＱＭ）（Ｇ３）も得ることができた。 [Comparative Example 4-2: Synthesis of Compounds G3 and G4]

Fullerene C ₆₀ (500 mg, 0.694 mmol), tetra n-butylammonium iodide (TBAI: 1.28 g, 3.47 mmol, 5 eq.), Toluene (230 mL) in a 500 mL three-necked eggplant flask under a nitrogen atmosphere ) After degassing under reduced pressure, the atmosphere was returned to a nitrogen atmosphere again, α, α′-dibromo-o-xylene (916 mg, 3.47 mmol, 5 eq.) Was added and the mixture was heated to reflux. After 10 hours, the temperature was returned to room temperature, applied to a silica gel filtration column (toluene), and concentrated. After being subjected to silica gel column chromatography (carbon disulfide: hexane = 1: 2), GPC purification (chloroform) was performed to obtain C as a regioisomer mixture in a yield of 47% (304 mg, 0.328 mmol). ₆₀ (QM) ₂ (G4) was obtained. By mass spectrometry (APCI method, negative), m / z: 928 [M ⁻ ] corresponding to the mass of the target product was detected. Since compound G3 is also produced as a by-product in the process of synthesizing compound G4, C ₆₀ (QM) (G3) could also be obtained by isolating this.

窒素雰囲気下、２００ｍＬ四口ナスフラスコに、Ｃ_７０（フロンティアカーボン社製， ５００ ｍｇ， ０．５９５ ｍｍｏｌ）、インデン（０．８２９ ｍＬ， ７．１４ ｍｍｏｌ）、及びｏ−ジクロロペンゼン（８０ ｍＬ）を加え、減圧脱気後、再び窒素雰囲気下に戻し、１８０℃で加熱還流した。１０時間後、インデン（１．６６ ｍＬ， １４．３ ｍｍｏｌ）を追加し、さらに２２時間加熱還流した。その後室温に戻し、溶媒を減圧留去した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（トルエン）に供した後、ＧＰＣ精製（クロロホルム）を行うことにより、Ｃ_７０（Ｉｎｄ）（化合物Ｇ５）を収率１１％（６５ ｍｇ， ０．０６８ ｍｍｏｌ）で、Ｃ_７０（Ｉｎｄ）_２（化合物Ｇ６）を収率２４％（１５０ ｍｇ， ０．１４０ ｍｍｏｌ）で、それぞれ位置異性体の混合物として得た。質量分析（ＡＰＣＩ法， ｎｅｇａｔｉｖｅ）により、化合物Ｇ５及び化合物Ｇ６のそれぞれについて、目的物の質量と一致するｍ／ｚ： ９５６［Ｍ⁻］及びｍ／ｚ： １０７２［Ｍ⁻］を検出した。 [Comparative Example 4-3: Synthesis of Compounds G5 and G6]

Under a nitrogen atmosphere, in a 200 mL four-necked eggplant flask, C ₇₀ (manufactured by Frontier Carbon, 500 mg, 0.595 mmol), indene (0.829 mL, 7.14 mmol), and o-dichlorobenzene (80 mL). ), Degassed under reduced pressure, and then returned again to a nitrogen atmosphere and heated to reflux at 180 ° C. After 10 hours, indene (1.66 mL, 14.3 mmol) was added, and the mixture was further heated to reflux for 22 hours. Thereafter, the temperature was returned to room temperature, and the solvent was distilled off under reduced pressure. The obtained crude product was subjected to silica gel column chromatography (toluene), followed by GPC purification (chloroform) to obtain C ₇₀ (Ind) (compound G5) in a yield of 11% (65 mg, 0.068). mmol) gave C ₇₀ (Ind) ₂ (Compound G6) in 24% yield (150 mg, 0.140 mmol) as a mixture of regioisomers, respectively. By mass spectrometry (APCI method, negative), m / z: 956 [M ⁻ ] and m / z: 1072 [M ⁻ ] corresponding to the mass of the target product were detected for each of compound G5 and compound G6.

<Example 5: LUMO measurement and solubility measurement of methanofullerene compound>
The LUMO of various methanofullerene compounds was calculated. The LUMO was calculated by the following cyclic voltammogram measurement method. Moreover, the solubility of various methanofullerene compounds was measured by the following solubility measurement method. The results are shown in Table 2. In addition, about PCBM and bis-PCBM, the thing by a frontier carbon company was used.

[Method of measuring cyclic voltammogram]
Cyclic voltammogram measurement was performed at room temperature, using a glassy carbon electrode as a working electrode, a platinum electrode as a counter electrode, and Ag / Ag ⁺ as a reference electrode. A mixed solution (4: 1, volume ratio) of o-dichlorobenzene and acetonitrile containing tetrabutylammonium perchlorate (TBAP) (0.1 M) was used as the electrolyte. The concentration of the methanofullerene compound was 0.5 mM. The potential was based on the oxidation-reduction potential of ferrocene. The LUMO value of PCBM (PCBM manufactured by Frontier Carbon Co., Ltd .: 1- (3-methoxycarbonyl) propyl-1-phenyl (6,6) -C ₆₀ ) Am. Chem. Soc. According to the description of 2008, 130, 15429-15436, it was set to -3.80 eV, and the LUMO value was calculated according to the relative value of the first reduction potential value obtained for each compound.

[Solubility measurement method]
The following method was used as a solubility measurement method. That is, each compound (fullerene compound) powder and toluene were mixed at 40 ° C. The amount of toluene used at this time was the minimum amount at which it was confirmed that each compound was dissolved at 40 ° C. Thereafter, the temperature of the solution was returned to 25 ° C. to confirm that there was no precipitation, and the concentration of the toluene solution at this time was taken as solubility. When precipitation was observed at 25 ° C., toluene was further added until dissolution, and the concentration of the toluene solution when dissolution was finally confirmed was taken as solubility.

  <Example 6: Polymer type organic thin film solar cell using methanofullerene compound as n-type semiconductor compound>

<Example 6-A1: Polymer-type organic thin-film solar cell using Compound A1 as an n-type semiconductor compound>
Regioregular poly-3-hexylthiophene (P3HT, manufactured by Rieke Metals) having an electron-donating molecular structure and compound A1 obtained in Synthesis Example 2-1 at a weight ratio of 1: 0.85 and 2.1% by weight At a concentration of o-dichlorobenzene. The obtained solution was stirred and mixed with a stirrer at 80 ° C. in a nitrogen atmosphere for 1 hour. The solution was filtered through a 0.45 μm polytetrafluoroethylene (PTFE) filter to prepare a photoelectric conversion layer coating solution.

  A glass substrate on which an indium tin oxide (ITO) transparent conductive film having a thickness of 155 nm was deposited was cleaned in the order of ultrasonic cleaning with a surfactant, water with ultrapure water, and ultrasonic cleaning with ultrapure water, and then nitrogen. It was dried by blow and dried by heating at 120 ° C. in the air for 5 minutes. Finally, ultraviolet ozone cleaning was performed.

On this transparent substrate, an aqueous dispersion of poly (3,4-ethylenedioxythiophene) poly (styrenesulfonic acid) filtered through a 0.45 μm polyvinylidene fluoride (PVDF) filter (manufactured by HC Starck Co., Ltd.) After spin-coating “CLEVIOUS ^™ PVP AI4083”), it was dried by heating at 120 ° C. in air for 10 minutes. Further, the substrate was heat-treated at 180 ° C. for 3 minutes in a nitrogen atmosphere. The film thickness was 40 nm.

  An active layer having a thickness of 200 nm was formed by applying the photoelectric conversion layer coating solution prepared as described above on a glass substrate under a nitrogen atmosphere by spin coating. Annealing treatment was performed at 150 ° C. for 10 minutes in a nitrogen atmosphere. Thereafter, calcium having a thickness of 10 nm and aluminum having a thickness of 80 nm were sequentially formed by resistance heating vacuum deposition to produce a 5 mm square bulk heterojunction organic thin film solar cell.

Using a solar simulator with air mass (AM) 1.5 and irradiance of 100 mW / cm ² as the irradiation light source, a 4 mm square metal mask is used to measure the current-voltage characteristics of the produced solar cell with a source meter (Type 2400 manufactured by Keithley). It was attached and measured. Table 3 shows the conversion efficiency.

<Example 6-B1: Polymer-type organic thin film solar cell using Compound A3 as an n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 6-1 except that the compound A3 obtained in Synthesis Example 2-2 was used in place of the compound A1 and an annealing treatment was performed at 160 ° C. for 10 minutes. Table 3 shows the conversion efficiency.

<Example 6-C1: Polymer-type organic thin film solar cell using Compound A5 as an n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 6-1 except that the compound A5 obtained in Synthesis Example 2-3 was used instead of the compound A1. Table 3 shows the conversion efficiency.

<Example 6-D1: Polymer-type organic thin film solar cell using Compound A10 as an n-type semiconductor compound>
Using Compound A10 obtained in Synthesis Example 2-4 instead of Compound A1, P3HT and Compound A10 were dissolved in o-dichlorobenzene at a weight ratio of 1: 0.95 at a concentration of 2.4% by weight and annealed. A solar cell was produced in the same manner as in Example 6-A1, except that the treatment was performed at 160 ° C. for 15 minutes. Table 3 shows the conversion efficiency.

<Comparative Example 6-A2: Polymer-type organic thin-film solar cell using compound G1 as an n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 6-A1, except that the compound G1 obtained in Comparative Example 4-1 was used instead of the compound A1. Table 3 shows the conversion efficiency.

<Comparative Example 6-A3: Polymer-type organic thin film solar cell using compound G2 as n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 6-A1 except that the compound G2 obtained in Comparative Example 4-1 was used instead of the compound A1. Table 3 shows the conversion efficiency.

<Comparative Example 6-B2: Polymer-type organic thin-film solar cell using compound G3 as an n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 6-A1 except that the compound G3 obtained in Comparative Example 4-2 was used instead of the compound A1. Table 3 shows the conversion efficiency.

<Comparative Example 6-B3: Polymer-type organic thin film solar cell using compound G4 as n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 6-A1 except that the compound G4 obtained in Comparative Example 4-2 was used instead of the compound A1. Table 3 shows the conversion efficiency.

<Comparative Example 6-C2: Polymer-type organic thin film solar cell using C ₆₀ PCB as an n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 6-A1 except that C ₆₀ PCBM (manufactured by Frontier Carbon Co.) was used instead of Compound A1. Table 3 shows the conversion efficiency.

<Comparative Example 6-C3: Polymer-type organic thin-film solar cell using C ₆₀ bisPCBM as an n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 6-A1 except that C ₆₀ bisPCBM (manufactured by Frontier Carbon Co.) was used instead of Compound A1. Table 3 shows the conversion efficiency.

<Comparative Example 6-D2: Polymer-type organic thin film solar cell using compound G5 as n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 6-A1 except that the compound G5 obtained in Comparative Example 4-3 was used instead of the compound A1. Table 3 shows the conversion efficiency.

<Comparative Example 6-D3: Polymer-type organic thin film solar cell using compound G6 as n-type semiconductor compound>
A solar cell was produced in the same manner as in Comparative Example 6-A1, except that Compound G6 obtained in Comparative Example 4-3 was used instead of Compound A1. Table 3 shows the conversion efficiency.

  From Table 3, in the case where a polymer material is used for the p-type semiconductor layer, each example having a dihydromethano group is compared with each comparative example having no dihydromethano group in the photoelectric conversion of the organic solar cell element. It can be seen that the efficiency (PCE) is improved.

<Example 7: Low molecular weight organic thin film solar cell using methanofullerene compound as n-type semiconductor compound>
First, a method for synthesizing a low molecular weight organic thin film solar cell material used in this example will be described.

[Synthesis Example 7-1: Synthesis of Compound H3]

窒素雰囲気下、冷却器を備えた５００ｍＬの４ツ口フラスコに、Ｅｔｈｙｌ−４，７−ｄｉｈｙｄｒｏ−８，８−ｄｉｍｅｔｈｙｌ−４，７−ｅｔｈａｎｏ−２Ｈ−ｉｓｏｉｎｄｏｌｅ−１−ｃａｒｂｏｘｙｌａｔｅ（Ｈ１）（５．００ｇ， ２０．４ ｍｍｏｌ）と、あらかじめ乳鉢ですりつぶした水酸化ナトリウム（６．２５ ｇ， １５０ ｍｍｏｌ）と、をエチレングリコール（１５０ ｍＬ）に溶解し、溶媒を脱気し窒素置換した。反応容器を遮光し、１７０℃で６０分撹拌し、室温に冷却した。反応溶液を氷水（３００ ｍＬ）に投入し、生成物をクロロホルムで抽出し、無水硫酸ナトリウムを添加して乾燥した。乾燥後、粉体をろ過し、ろ液を減圧濃縮した。濃縮によって得られたオイルを昇華精製し、ジメチルビシクロピロール誘導体（Ｈ２）（２．５４ ｇ， １４．７ ｍｍｏｌ， ７２ ％）を得た。得られた化合物が目的のジメチルビシクロピロール誘導体（Ｈ２）であることを、^１Ｈ ＮＭＲで確認した。 [Synthesis Example 7-1-1: Synthesis of Intermediate H2]

Under a nitrogen atmosphere, in a 500 mL four-necked flask equipped with a condenser, Ethyl-4,7-dihydro-8,8-dimethyl-4,7-ethano-2H-isoindole-1-carboxylate (H1) (5. 00 g, 20.4 mmol) and sodium hydroxide (6.25 g, 150 mmol) previously ground in a mortar were dissolved in ethylene glycol (150 mL), and the solvent was degassed and replaced with nitrogen. The reaction vessel was shielded from light, stirred at 170 ° C. for 60 minutes, and cooled to room temperature. The reaction solution was poured into ice water (300 mL), the product was extracted with chloroform, and dried by adding anhydrous sodium sulfate. After drying, the powder was filtered and the filtrate was concentrated under reduced pressure. The oil obtained by concentration was purified by sublimation to obtain a dimethylbicyclopyrrole derivative (H2) (2.54 g, 14.7 mmol, 72%). It was confirmed by ¹ H NMR that the obtained compound was the target dimethylbicyclopyrrole derivative (H2).

Dimethylbicyclopyrrole derivative (H2): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.46 (br s, 1H), 6.54 (m, 1H), 6.48 (m, 1H), 6.47 (M, 1H), 6.41 (m, 1H), 3.70 (m, 1H), 3.22 (d, 1H, J = 5.9 Hz), 1.41 (dd, 1H, J = 11.5, 2.7 Hz), 1.24 (dd, 1H, J = 11.5, 2.7 Hz), 1.04 (s, 3H), and 0.72 (s, 3H).

合成例７−１−１で合成した中間体Ｈ２（３．８１ ｇ， ２２ ｍｍｏｌ）をクロロホルム（アミレン含有）（４００ ｍＬ）に溶解し、これに窒素雰囲気下でパラホルムアルデヒド（８５０ ｍｇ）を添加し、ついでｐ−トルエンスルホン酸一水和物（２００ ｍｇ）を添加し、室温で５時間撹拌した。続いてｐ−クロラニル（２．１７ ｇ）を添加してさらに５時間撹拌した。反応液を水に注入し、有機層を分離して飽和炭酸水素ナトリウム溶液、水、食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。粉体をろ過後、ろ液を減圧濃縮し、残渣をクロロホルム溶媒としてまずアルミナのカラムクロマトグラフィーで精製し、ついでシリカゲルクロマトグラフィーで酢酸エチル／クロロホルムで精製することで、目的の位置異性体から構成されるビシクロポルフィリン化合物の混合物（Ｈ３）（２．４４ ｇ， ３．３０ ｍｍｏｌ， ６０ ％）が得られた。 [Synthesis Example 7-1-2: Synthesis of Compound H3]

Intermediate H2 (3.81 g, 22 mmol) synthesized in Synthesis Example 7-1-1 was dissolved in chloroform (containing amylene) (400 mL), and paraformaldehyde (850 mg) was added thereto under a nitrogen atmosphere. Then, p-toluenesulfonic acid monohydrate (200 mg) was added, and the mixture was stirred at room temperature for 5 hours. Subsequently, p-chloranil (2.17 g) was added and further stirred for 5 hours. The reaction solution was poured into water, the organic layer was separated, washed with saturated sodium bicarbonate solution, water and brine, and dried over anhydrous sodium sulfate. After filtration of the powder, the filtrate was concentrated under reduced pressure, and the residue was first purified by alumina column chromatography using chloroform as the solvent, and then purified by silica gel chromatography with ethyl acetate / chloroform to form the desired regioisomer. Of the resulting bicycloporphyrin compound (H3) (2.44 g, 3.30 mmol, 60%) was obtained.

It was confirmed by ¹ H NMR, LC analysis, and MS analysis that the obtained compound was an isomer mixture (H3) of the target bicycloporphyrin compound. Various analysis results are shown below. The LC analysis results are shown in Table 4. By mass spectrometry (FAB-MS method), m / z: 736 [M ⁺ ] corresponding to the mass of the target product was detected.
¹ H NMR (400 MHz, CDCl ₃ ) δ 10.26-10.33 (m, 4H), 7.11-7.26 (m, 8H), 5.63 (m, 4H), 5.12- 5.16 (m, 4H), 2.06-2.11 (m, 4H), 1.75-1.88 (m, 4H), 1.55-1.56 (m, 12H), 0. 59-0.80 (m, 12H), and -4.63 (br s, 2H).

特開２００３−３０４０１４号公報における明細書段落［００６０］〜［００６６］のの記載を元に合成した。すなわち、以下のようにして化合物Ｈ４を合成した。 [Synthesis Example 7-2: Synthesis of Compound H4]

This was synthesized based on the descriptions in paragraphs [0060] to [0066] in Japanese Patent Application Laid-Open No. 2003-304014. That is, Compound H4 was synthesized as follows.

  Thiophenol (53.5 mL) and potassium hydroxide (51.25 g) were dissolved in ethanol (600 mL). To this solution, cis-1,2-dichloroethylene (19.4 mL) was slowly added dropwise. Thereafter, the mixture was stirred at room temperature for 30 minutes, and further heated and stirred at 80 to 90 ° C. for 23 hours. The solvent was concentrated under reduced pressure, water was added thereto, and the mixture was extracted with chloroform. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain cis-1,2-phenylthioethylene.

  The obtained cis-1,2-phenylthioethylene and diphenyl diselenide (750 mg) were dissolved in methylene chloride (100 mL). The solution was cooled in an ice bath and 30% aqueous hydrogen peroxide (175 mL) was added slowly. The crystals precipitated by vigorous stirring overnight at room temperature were filtered off, dissolved in chloroform, washed with water, saturated aqueous sodium hydrogen carbonate, and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Further, this was dissolved in chloroform (500 mL), m-chloroperbenzoic acid (84 g) was slowly added while cooling in an ice bath, and the mixture was stirred overnight at room temperature. The precipitated solid was filtered through Celite, and the organic layer was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. This solid was rinsed with ether to give cis-1,2-diphenylsulfonylethylene (67.06 g, 87%). Colorless crystals, mp 100-101 ° C.

  Cis-1,2-diphenylsulfonylethylene and a catalytic amount of iodine were dissolved in methylene chloride, and what was deposited as a solid by irradiation with sunlight was filtered to obtain trans-1,2-diphenylsulfonylethylene. Colorless crystals, mp 219.5 ° C.

  Trans-1,2-diphenylsulfonylethylene (29.33 g) is dissolved in toluene (200 mL), and then 1,3-cyclohexadiene (11.4 mL) is added, followed by dry distillation for 21 hours, followed by recrystallization. This gave 5,6-diphenylsulfonyl-bicyclo- [2,2,2] oct-2-ene (35.66 g, 96.5%).

  5,6-Diphenylsulfonyl-bicyclo- [2,2,2] oct-2-ene (7.76 g) is placed in a reaction vessel, purged with nitrogen, and dissolved in anhydrous tetrahydrofuran (THF) (50 mL). I let you. Thereto was added ethyl isocyanoacetate (2.43 mL), the reaction solution was cooled in an ice bath, and a 1M solution of t-BuOK / THF (50 mL) was slowly added dropwise. Thereafter, the reaction solution was returned to room temperature and stirred overnight. Quenched with 1N hydrochloric acid, extracted with chloroform, washed with water and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel chromatography to obtain 4,7-dihydro-4. , Ethyl 7-ethano-2H-isoindole-1-carboxylate (3.49 g, 80.4%) was obtained. Colorless crystals, mp 129-130 ° C.

LiAlH ₄ (0.144 g) was added to a solution of ethyl 4,7-dihydro-4,7-ethano-2H-isoindole-1-carboxylate (0.109 g) in THF (15 mL). The mixture was added dropwise with stirring at 0 ° C., and stirred at 0 ° C. for 2 hours. The reaction mixture was poured into saturated brine (25 mL) and extracted three times with chloroform (50 mL). P-Toluenesulfonic acid (0.010 g) was added to the combined extract and stirred at room temperature for 12 hours. p-Chloranil (0.150 g) was added, and after stirring at room temperature for 12 hours, the reaction solution was poured into water. The organic phase was separated, washed 5 times with aqueous sodium hydrogen carbonate solution (250 mL), once with water (250 mL), and with saturated brine (100 mL), and then dried over magnesium sulfate. The residue obtained by distilling off the solvent by distillation was purified by column chromatography (chloroform, alumina), and the porphyrin compound Tetrakis (bicyclo [2.2.2] octadiene) porphyrin (H4) (0.094 g) containing the target bicyclo structure. )

The LC analysis results are shown in Table 4. By mass spectrometry (FAB-MS method), m / z: 623 [M ⁺ +1] consistent with the mass of the target product was detected.
¹ H NMR (400 MHz, CDCl ₃ ) δ 10.40 (m, 4H), 7.20 (m, 8H), 5.81 (m, 8H), 2.24 (m, 8H), and -4 .80 (br s, 2H).

[Synthesis Example 7-3: Synthesis of Compound H8]

[Synthesis Example 7-3-1: Synthesis of Intermediate H7]

  In a nitrogen atmosphere, 1-bromopyrene (Tokyo Kasei) (H5) (5.6 g, 20 mmol) was dissolved in dehydrated THF (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 45 minutes while maintaining -78 ° C. Subsequently, triphenyl phosphite (Wako Pure Chemical Industries, Ltd.) (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 again to -78 ° C. did. On the other hand, 4-trifluoromethylbromobenzene (Tokyo Kasei) (H6) (4.4 g, 20 mmol) was dissolved in dehydrated THF (50 mL) in a separate reaction vessel, and the temperature was −78 ° C. under a nitrogen atmosphere. Then, n-BuLi (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 further stirred for 1 hour.

Water (20 mL) was added to the obtained reaction solution, THF was distilled off under reduced pressure, and extraction was performed using methylene chloride. Magnesium sulfate is added to the organic layer, dried, concentrated by filtration, and purified using column chromatography (developing solvent: hexane) to give CF ₃ -PPy ₂ (H7) (2.9 g, 50%). Obtained. In addition, the identification of the compound was performed using NMR.

[Synthesis Example 7-3-2: Synthesis of Compound H8]

Intermediate H7 (2.9 g) obtained above was dissolved in acetone (Kanto Chemical) (150 mL), hydrogen peroxide solution (Wako Pure Chemicals, 30% by weight) (2 mL) was added, and the mixture was stirred at room temperature. did. Water (20 mL) was added to the reaction solution, concentrated, and then washed with acetonitrile to obtain CF ₃ -POPy ₂ (H8) (2.4 g, 80%). The resulting product was confirmed by NMR.

[Synthesis Example 7-4: Synthesis of Compound H10]

５００ｍＬ三口ナスフラスコに、窒素雰囲気下、臭化２−メトキシフェニルマグネシウムの１．０Ｍ ＴＨＦ溶液（１００ ｍＬ， ０．１ ｍｏｌ）を入れて室温で攪拌した。ここに、クロロメチルジメチルクロロシラン（１１．２５ ｍＬ， ０．０８５ ｍｏｌ）をゆっくり滴下した。室温で１時間攪拌後、４０℃で３時間攪拌した。室温に戻し、ゆっくりと水を加えた。酢酸エチルで抽出し、食塩水洗浄後、硫酸ナトリウム上で乾燥、ろ過し、減圧下濃縮した。得られた液体を減圧蒸留することにより、クロロメチル（２−メトキシフェニル）ジメチルシラン（（ｏ−Ａｎ）Ｍｅ_２ＳｉＣＨ_２Ｃｌ）（Ｈ９）（１１．２ ｇ， ０．０５２２ ｍｏｌ， ５２ ％）を無色液体として得た。 [Synthesis Example 7-4-1: Synthesis of Intermediate H9]

In a 500 mL three-necked eggplant flask, a 1.0 M THF solution (100 mL, 0.1 mol) of 2-methoxyphenylmagnesium bromide was placed in a nitrogen atmosphere and stirred at room temperature. Chloromethyldimethylchlorosilane (11.25 mL, 0.085 mol) was slowly added dropwise thereto. After stirring at room temperature for 1 hour, the mixture was stirred at 40 ° C. for 3 hours. It returned to room temperature and water was added slowly. The mixture was extracted with ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The obtained liquid was distilled under reduced pressure to obtain chloromethyl (2-methoxyphenyl) dimethylsilane ((o-An) Me ₂ SiCH ₂ Cl) (H9) (11.2 g, 0.0522 mol, 52%) Was obtained as a colorless liquid.

窒素雰囲気下、Ｎ，Ｎ−ジメチルホルムアミド（６．４５ ｍＬ， ８３．３ ｍｍｏｌ）、フラーレンＣ_６０（Ｅ０）（２．００ ｇ， ２．７８ ｍｍｏｌ）、１，２−ジクロロベンゼン（５００ ｍＬ）を混合し、脱気した後、窒素で復圧した。ここに、（クロロメチル）ジメチルフェニルシランから調製したＧｒｉｇｎａｒｄ試薬（ＰｈＭｅ_２ＳｉＣＨ_２ＭｇＣｌ， ９．８０ ｍＬ， ０．８５０ Ｍ， ８．３３ ｍｍｏｌ）のＴＨＦ溶液を２５℃で加えた。１０分間攪拌した後、脱気した飽和塩化アンモニウム水溶液（１．０ ｍＬ）を加え攪拌した。得られた溶液を濃縮した後，トルエン（２００ ｍＬ）に溶解させ、シリカゲルろ過カラムを通した後、濃縮した。メタノール（１００−２００ ｍＬ）を加え、再沈させることにより茶色の固体を得た。得られた固体をＨＰＬＣ（Ｂｕｃｋｙｐｒｅｐ ｃｏｌｕｍｎ， ｅｌｕｅｎｔ： ｔｏｌｕｅｎｅ／２−ｐｒｏｐａｎｏｌ ＝ ７／３）で分取することにより、目的物である１−（ジメチルフェニルシリルメチル）−１，９−ジヒドロ（Ｃ_６０−Ｉ_ｈ）［５，６］フラーレン（Ｃ_６０（ＣＨ_２ＳｉＭｅ_２Ｐｈ）Ｈ）（Ｅ４）（１．９９ ｇ， ２．２８ ｍｍｏｌ， ８２％ ｉｓｏｌａｔｅｄ ｙｉｅｌｄ， ａｎａｌｙｔｉｃａｌｌｙ ｐｕｒｅ）を得た。 [Synthesis Example 7-4-2: Synthesis of Intermediate E4]

Under a nitrogen atmosphere, N, N-dimethylformamide (6.45 mL, 83.3 mmol), fullerene C ₆₀ (E0) (2.00 g, 2.78 mmol), 1,2-dichlorobenzene (500 mL) Were mixed, degassed, and then re-pressured with nitrogen. To this was added a THF solution of Grignard reagent (PhMe ₂ SiCH ₂ MgCl, 9.80 mL, 0.850 M, 8.33 mmol) prepared from (chloromethyl) dimethylphenylsilane at 25 ° C. After stirring for 10 minutes, a degassed saturated aqueous ammonium chloride solution (1.0 mL) was added and stirred. The resulting solution was concentrated, dissolved in toluene (200 mL), passed through a silica gel filtration column, and concentrated. Methanol (100-200 mL) was added and reprecipitated to obtain a brown solid. The obtained solid was fractionated by HPLC (Buckyprep column, eluent: toluene / 2-propanol = 7/3) to obtain 1- (dimethylphenylsilylmethyl) -1,9-dihydro (C ₆₀ -I _h) [5,6] fullerene _{(C 60 (CH 2 SiMe 2} Ph) H) (E4) (1.99 g, 2.28 mmol, 82% isolated yield, was obtained analytically pure).

窒素雰囲気下、中間体Ｅ４（１．０２ ｇ， １．１７ ｍｍｏｌ）のベンゾニトリル溶液を脱気した後、ｔ−ブトキシカリウム（１．４１ ｍＬ， １．０ Ｍ， １．４１ ｍｍｏｌ）のＴＨＦ溶液を２５℃で加えた。１０分間攪拌した後，中間体Ｈ９（５．０３ ｇ， ２３．４ ｍｍｏｌ）とヨウ化カリウム（３．８８ ｇ， ２３．４ ｍｍｏｌ）を加え、１１０℃で１７時間攪拌した。得られた溶液に飽和塩化アンモニウム水溶液（１．０ ｍＬ）を加え，濃縮した。得られた粗生成物にトルエン（１００ ｍＬ）を加え、ろ過濃縮した後、メタノール（５０−１００ ｍＬ）を加え、再沈を行った。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ｅｌｕｅｎｔ： ＣＳ_２／ｈｅｘａｎｅ ＝ １／１）精製に供し、続いてＨＰＬＣ分取（Ｂｕｃｋｙｐｒｅｐ ｃｏｌｕｍｎ， ｅｌｕｅｎｔ： ｔｏｌｕｅｎｅ／２−ｐｒｏｐａｎｏｌ ＝ ７／３）精製を行うことにより、目的物（Ｃ_６０（ＣＨ_２ＳｉＭｅ_２Ｐｈ）［ＣＨ_２ＳｉＭｅ_２（ｏ−Ａｎ）］）（ＳＩＭＥＦ２）（Ｈ１０）（０．８１０ ｇ， ０．７７２ ｍｍｏｌ， ６６％ ｉｓｏｌａｔｅｄ ｙｉｅｌｄ） を得た。 [Synthesis Example 7-4-3: Synthesis of Compound H10]

After degassing a benzonitrile solution of intermediate E4 (1.02 g, 1.17 mmol) under nitrogen atmosphere, potassium t-butoxy (1.41 mL, 1.0 M, 1.41 mmol) in THF. The solution was added at 25 ° C. After stirring for 10 minutes, Intermediate H9 (5.03 g, 23.4 mmol) and potassium iodide (3.88 g, 23.4 mmol) were added, and the mixture was stirred at 110 ° C. for 17 hours. Saturated aqueous ammonium chloride solution (1.0 mL) was added to the resulting solution and concentrated. Toluene (100 mL) was added to the obtained crude product, and after concentration by filtration, methanol (50-100 mL) was added to perform reprecipitation. The obtained crude product was subjected to silica gel column chromatography (eluent: CS ₂ / hexane = 1/1) purification, followed by HPLC fractionation (Buckyprep column, eluent: toluene / 2-propanol = 7/3) purification. it allows the desired product to perform _{(C 60 (CH 2 SiMe 2} Ph) [CH 2 SiMe 2 (o-An)]) (SIMEF2) (H10) (0.810 g, 0.772 mmol, 66% isolated yield) Got.

<Example 7-1: Low molecular weight organic thin-film solar cell using Compound A1 as an n-type semiconductor compound>
A poly (3,4-ethylenedioxythiophene) poly (styrenesulfonic acid) aqueous dispersion (manufactured by H.C. Starck, Inc., trade name “CLEVIOUS ^™ PVP” as a hole extraction layer on a glass substrate on which an ITO electrode is patterned. AI4083 ") was applied by spin coating, and then the substrate was heated on a hot plate at 120 ° C for 10 minutes in the air. The film thickness of the hole extraction layer was about 30 nm.

The substrate was first heat-treated at 180 ° C. for 3 minutes under a nitrogen atmosphere, and then a toluene solution containing 0.4 wt% of the coating conversion type bicycloporphyrin compound (H3) produced in Synthesis Example 7-1 was filtered. It apply | coated by spin-coating at 1500 rpm on the said board | substrate. By heating the substrate at 195 ° C. in a nitrogen atmosphere, a layer of p-type semiconductor compound tetrabenzoporphyrin (BP) (H11) having a thickness of about 25 nm was formed on the hole extraction layer.

  Chloroform: chlorobenzene = 1 containing 0.75% by weight of the coating conversion type bicycloporphyrin compound (H4) produced in Synthesis Example 7-2 and 1.75% by weight of Compound H10 (SIMEF2) synthesized in Synthesis Example 7-4 A 1 (weight ratio) solution was prepared, filtered, and the filtrate obtained under a nitrogen atmosphere was spin coated at 1500 rpm and heated at 170 ° C. for 30 minutes. As a result, a mixture layer containing tetrabenzoporphyrin (H11) and SIMEF2 (H10) of about 100 nm was formed on the p-type semiconductor compound layer.

  Next, a solution prepared by dissolving 0.65% by weight of Compound A1 in toluene is prepared, filtered, and the filtrate obtained in a nitrogen atmosphere is spin-coated on the mixture layer at 3000 rpm, followed by heat treatment at 120 ° C. for 5 minutes. gave. As a result, compound H10 (SIMEF2) in the mixture layer was replaced with compound A1, and a layer of compound A1 was formed on the tetrabenzoporphyrin (H11) layer.

  Subsequently, the compound H8 synthesized in Synthesis Example 7-3 was placed in a metal boat placed in a vacuum deposition apparatus, heated, and the compound H8 was deposited on the layer of the compound A1 until the film thickness reached 4.5 nm. . Thus, an electron extraction layer was formed on the layer of Compound A1.

  Furthermore, an aluminum electrode having a thickness of 80 nm was provided on the electron extraction layer by vacuum deposition, and then this solar cell was heated on a hot plate at 200 ° C. for 5 minutes to produce a photoelectric conversion element.

A solar cell sealed using a glass plate as a sealing plate was irradiated with light of 100 mW / cm ^{2 with} a solar simulator (AM1.5G) from the ITO electrode side, and a source meter (Caysley, Model 2400) The current-voltage characteristics between the ITO electrode and the aluminum electrode were measured. Table 5 shows the conversion efficiency.

<Example 7-2: Low molecular weight organic thin-film solar cell using Compound A3 as an n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 7-1 except that Compound A3 obtained in Synthesis Example 2-2 was used instead of Compound A1. Table 5 shows the conversion efficiency.

<Example 7-3: Low molecular weight organic thin-film solar cell using Compound A5 as an n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 7-1 except that Compound A5 obtained in Synthesis Example 2-3 was used instead of Compound A1. Table 5 shows the conversion efficiency.

<Example 7-4: Low molecular weight organic thin film solar cell using Compound A7 as an n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 7-1 except that Compound A7 obtained in Synthesis Example 3-2 was used instead of Compound A1. Table 5 shows the conversion efficiency.

<Comparative Example 7-5: Low molecular weight organic thin film solar cell using C ₆₀ PCBM as n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 7-1 except that C ₆₀ PCBM (manufactured by Frontier Carbon Co.) was used instead of Compound A1. Table 5 shows the conversion efficiency.

<Comparative Example 7-6: Low-molecular organic thin-film solar cell using C ₆₀ bisPCBM as an n-type semiconductor compound>
A solar cell was produced in the same manner as in Example 7-1 except that C ₆₀ bisPCBM (manufactured by Frontier Carbon Co.) was used instead of Compound A1. Table 5 shows the conversion efficiency.

  From Table 5, even when a low molecular weight compound is used as the p-type semiconductor compound, in the examples in which the compound having a dihydromethano group was used as the n-type semiconductor compound, the compound having no dihydromethano group was an n-type. It turns out that the photoelectric conversion efficiency (PCE) of an organic solar cell element is improving compared with the comparative example used as a semiconductor compound.

DESCRIPTION OF SYMBOLS 100 Photoelectric conversion element 110 Substrate 120 Electrode 130 Hole taking-out layer 140 Active layer 150 Electron taking-out layer 160 Electrode 1 Weatherproof protective film 2 Ultraviolet cut film 3, 9 Gas barrier film 4, 8 Getter material film 5, 7 Sealing material 6 Sun Battery element 10 Back sheet 11 Sealing material 12 Base material 13 Solar cell module 14 Thin film solar cell

Claims (14)

A photoelectric conversion element comprising at least a pair of electrodes and an active layer, wherein the active layer contains a fullerene compound substituted with one or more dihydromethano groups and one or more organic groups, A photoelectric conversion element comprising one or more organic groups represented by the following formulas (n1) to (n7):

In the above formulas (n1) to (n7), FLN represents fullerene. The carbon atom on the fullerene to which the organic group is bonded is located in the same 5-membered ring or 6-membered ring in the fullerene skeleton. r, s, t, u, v, w, and x are independent integers of 0 or more, and the sum of r, s, t, u, v, w, and x is 1 or more and 5 or less.
In the formula (n1), L is an integer of 1 to 8, and R ¹ is an alkyl group having 1 to 14 carbon atoms that may have a substituent, and 1 carbon atom that may have a substituent. Or an aromatic group which may have a substituent, and R ^{2 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an alkyl group having 1 to 14 carbon atoms. The fluorinated alkyl group or an aromatic group which may have a substituent.
In formula (n2), R ^{5 to} R ⁹ 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.
In formula (n3), Ar ¹ is an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 2 to 20 carbon atoms, and R ^{10 to} R ^13. Each independently has a hydrogen atom, an alkyl group which may have a substituent, an amino group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An alkylthio group which may be used. R ¹⁰ or R ¹¹ may form a ring with R ¹² or R ¹³ .
In formula (n4), one of R ¹⁴ and R ¹⁵ may have a hydrogen atom, an alkoxycarbonyl group, an alkyl group having 1 to 14 carbon atoms which may have a substituent, or a substituent. The other is an aromatic group, and the other is an alkoxycarbonyl group, an alkyl group having 1 to 14 carbon atoms which may have a substituent, or an aromatic group which may have a substituent.
In the formula (n5), Ar ² and Ar ³ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or 2 carbon atoms which may have a substituent. -20 aromatic heterocyclic groups.
In the formula (n6), Ar ⁴ and Ar ⁵ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or 2 carbon atoms which may have a substituent. -20 aromatic heterocyclic groups.
In formula (n7), R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 14 carbon atoms which may have a substituent, or an aromatic group which may have a substituent. .   The photoelectric conversion element according to claim 1, wherein the active layer contains a fullerene compound substituted with an organic group represented by the formula (n3).   The photoelectric conversion device according to claim 1, wherein the active layer contains a fullerene compound substituted with an organic group represented by the formula (n4).   The photoelectric conversion element according to claim 1, wherein the active layer contains a fullerene compound substituted with an organic group represented by the formula (n7).   The photoelectric conversion device according to any one of claims 1 to 4, wherein the fullerene compound has one dihydromethano group. A method for producing a fullerene compound represented by the following formula (A-II), comprising a reaction step of causing an oxidizing agent to act on the fullerene compound represented by the following formula (B-II).

In the above formula, fln represents a fullerene to which an organic group may be added. m ″ ′ is 1 or 2, m ′ is 0 or 1, m ″ is 1 or 2, and m ′ ″ is the sum of m ′ and m ″.
In the above formula, the dihydromethano group is bonded to the same 5-membered ring or 6-membered ring in the fullerene skeleton. A combination of a hydrogen atom and a silylmethyl group is also bonded on the same five-membered or six-membered ring on the fullerene ring.
In formula (B-II), R ^{21 to} R ²³ each independently have a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a substituent. An alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms which may have a substituent, an amino group which may have a substituent, and a silyl which may have a substituent Group, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an aryl which may have a substituent A sulfonyl group.   The method for producing a fullerene compound according to claim 6, wherein a basic compound is used in combination in the reaction step. A method for producing a fullerene compound represented by the following formula (A-II), comprising a step of cleaving a bond between fullerenes of a fullerene dimer.

In the above formula, fln represents a fullerene to which an organic group may be added, and m ′ ″ is 1 or 2. The said fullerene dimer is represented by the following Formula (C-II), The manufacturing method of the fullerene compound of Claim 8 characterized by the above-mentioned.

In the above formula, fln represents a fullerene to which an organic group may be added. m ′ is 0 or 1, and m ′ ″ = m ′ + 1.
In the above formula, the dihydromethano group is bonded to the same 5-membered ring or 6-membered ring in the fullerene skeleton. A pair of one fullerene and a silylmethyl group is also bonded on the same five-membered or six-membered ring on the other fullerene ring.
R ^{24 to} R ²⁶ are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, or an optionally substituted alkoxy group having 1 to 30 carbon atoms. An aryloxy group having 6 to 30 carbon atoms which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, and a substituent. An alkylthio group which may have a substituent, an arylthio group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent. Each of R ^{24 to} R ²⁶ substituted on the silyl group of one fullerene is the same as or different from each of R ^{24 to} R ²⁶ substituted on the silyl group of the other fullerene. Yes.   10. The method for producing a fullerene compound according to claim 8, wherein an oxidizing agent is allowed to act on the fullerene dimer in the cleavage step.   The method for producing a fullerene compound according to claim 6 or 10, wherein the oxidizing agent is a metal salt.   The method for producing a fullerene compound according to claim 11, wherein the oxidizing agent is a divalent copper salt. A fullerene compound represented by the following formula (n11):

In the above formula, FLN represents fullerene. The dihydromethano group is bonded to the same 5-membered ring or 6-membered ring in the fullerene skeleton. t ′ is an integer of 1 to 5.
In the above formula, Ar ^{1 ′} is an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group having 3 to 10 carbon atoms, and R ^{10 ′ to} R ^{13 ′} are each independently , A hydrogen atom, an oxygen atom, a sulfur atom, an alkyl group which may have a substituent, an amino group which may have a substituent, or an alkoxy group which may have a substituent. R ^{10 ′} or R ^{11 ′} may form a ring with R ^{12 ′} or R ^{13 ′} . A fullerene compound represented by the following formula (n12):

In the above formula, FLN represents fullerene. The dihydromethano group is bonded to the same 5-membered ring or 6-membered ring in the fullerene skeleton. u ′ is an integer of 1 to 5.
In the above formula, one of R ^{14 ′} and R ^{15 ′} may have a hydrogen atom, an alkoxycarbonyl group, an alkyl group having 1 to 14 carbon atoms which may have a substituent, or a substituent. The other is an aromatic group, and the other is an alkoxycarbonyl group, an alkyl group having 1 to 14 carbon atoms which may have a substituent, or an aromatic group which may have a substituent.

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