JP5499193B2 - Organic thin film solar cell - Google Patents

Description

  The present invention relates to an organic thin film solar cell. More specifically, the present invention relates to an organic thin film solar cell having an organic solid multilayer portion between a pair of electrodes.

  An organic thin film solar cell is a device that shows an electrical output with respect to an optical input, as represented by a photodiode or an imaging device that converts an optical signal into an electrical signal, or a solar cell that converts optical energy into electrical energy, It is a device that exhibits a response opposite to that of an electroluminescence (EL) element that exhibits an optical output with respect to an electrical input. In particular, solar cells have attracted a great deal of attention as a clean energy source in recent years against the background of fossil fuel depletion and global warming, and research and development have been actively conducted.

  Conventionally, silicon solar cells represented by single crystal Si, polycrystal Si, amorphous Si, etc. have been put into practical use. However, as the cost and raw material Si shortage problems surface, The demand for next generation solar cells is increasing. Against this background, organic solar cells are attracting much attention as next-generation solar cells next to silicon-based solar cells because they are inexpensive, have low toxicity, and do not have a fear of shortage of raw materials.

Organic solar cells are basically composed of an n layer for transporting electrons and a p layer for transporting holes, and is roughly classified into two types depending on the material constituting each layer.
A solar cell in which a sensitizing dye such as ruthenium dye is adsorbed on the surface of an inorganic semiconductor such as titania as the n layer and an electrolyte solution is used as the p layer is called a dye sensitized solar cell (so-called Gretzell cell), and has a conversion efficiency. However, since the solution has been used since 1991, it has a drawback such as liquid leakage when used for a long time. In order to overcome these drawbacks, research has been recently conducted to find an all-solid-state dye-sensitized solar cell by solidifying the electrolyte solution. However, a technique for soaking organic matter into the pores of porous titania is known. At present, a cell having a high degree of difficulty and high reproducibility and high conversion efficiency has not been completed.
On the other hand, organic thin-film solar cells consisting of organic thin films in both the n-layer and p-layer are all solid, so they have no drawbacks such as liquid leakage, are easy to manufacture, and do not use ruthenium, which is a rare metal. Attracted attention and researched energetically.

  Organic thin-film solar cells have been researched with single-layer films using merocyanine dyes, etc., but it has been found that conversion efficiency can be improved by using p-layer / n-layer multilayer films. Multilayer films are becoming mainstream. The materials used at this time were copper phthalocyanine (CuPc) for the p layer and peryleneimides (PTCBI) for the n layer.

  Subsequently, it has been found that the conversion efficiency is improved by inserting an i layer (a mixed layer of p material and n material) between the p layer and the n layer to increase the number of layers.

In organic thin-film solar cells using polymers, conductive polymers are used as the p material, C ₆₀ derivatives are used as the n material, and they are mixed and heat-treated to induce micro-layer separation to form heterointerfaces. Research on so-called bulk heterostructures has been mainly conducted to increase the conversion efficiency and improve the conversion efficiency. Here material system that has been used primarily soluble polythiophene derivative called P3HT as p material was soluble C ₆₀ derivatives referred to as PCBM as an n material.

  In general, the operation process of an organic thin film solar cell consists of (1) light absorption and exciton generation, (2) exciton diffusion, (3) charge separation, (4) carrier movement, and (5) electromotive force generation. ing. In general, organic substances have few absorption characteristics that match the solar spectrum, and carrier mobility is often low, so high conversion efficiency cannot often be achieved.

From the viewpoint of improving device performance, a multilayer configuration in which a new functional layer is introduced has been proposed.
Specifically, a configuration in which a phenanthroline derivative typified by BCP is introduced as an organic blocking layer or an exciton blocking layer at the interface with an electrode has been proposed (Patent Document 1).
Although the solar cell of Patent Document 1 is an organic multilayer type, it is a technology limited to phenanthroline derivatives, and an element using the derivative has a problem that storage characteristics are poor and performance changes with time are large.

  The solar cell of Patent Document 2 is an organic single layer type. In the examples, the performance is storage stability, and there is no disclosure about efficiency. In addition, using a compound in which an electron-donating molecular structure and an electron-accepting molecular structure are combined with a non-conjugated molecular structure, using a photo-induced electron transfer reaction between the electron-donating molecular structure and the electron-accepting molecular structure, Charge separation is generated. In the case of such a single layer configuration, when the same molecule is connected to both of the pair of electrodes and is contacted in the organic layer to form a charge transport path, the current in the direction opposite to the current due to the electromotive voltage is formed inside the device. May occur, which is an impediment to the original device performance, and the performance may not be improved.

  Non-Patent Document 1 discloses a solar cell including a layer that serves as a charge separation layer of excitons, but does not contact the electrode and cannot improve charge extraction efficiency.

Special table 2008-522413 gazette International Publication No. 03/073323 Pamphlet

Adv.Mater., 18, 2872 (2006)

  An object of the present invention is to provide an organic thin-film solar cell having excellent photoelectric conversion efficiency and little change in battery characteristics over time.

（式中、Ｄは、電子供与性置換基である。
Ａは、電子受容性置換基である。
Ａｒは、それぞれ置換若しくは無置換のアリーレン基、又は置換若しくは無置換のヘテロアリーレン基である。
Ｖは、それぞれ置換若しくは無置換のビニレン基、又は置換若しくは無置換のアゾメチン基である。
ｐ、ｑ及びｒは、それぞれ０〜３の整数である。
Ｄ及びＡｒ並びにＶ及びＡは、それぞれ互いに結合して環構造を形成してもよい。）
３．前記式（１）で表される化合物のＡｒがフェニレン基、ナフタレニル基又はアントラセニレン基であり、Ｖがビニレン基であり、ｐ、ｑ及びｒがそれぞれ１〜２の整数であり、電子供与性置換基Ｄが置換若しくは無置換の水酸基、又は置換若しくは無置換のアミノ基であり、電子受容性置換基Ａがニトロ基、シアノ基又は下記式（２）で表される置換基である２に記載の有機薄膜太陽電池。

（式中、Ｘは、酸素原子、又はＮＲ^２であり、
Ｒ^２は、水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基である。
Ｒは、水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、置換若しくは無置換の炭素数１〜２０のアリール基、置換若しくは無置換の炭素数１〜６のアルコキシ基、置換若しくは無置換の炭素数６〜２０のアリールオキシ基、置換若しくは無置換の炭素数１〜６のアルキルアミノ基、又は置換若しくは無置換の炭素数６〜２０のアリールアミノ基である。）
４．前記１以上の電子供与性構造Ｄ及び１以上の電子受容性構造Ａを有するπ電子共役系分子骨格Ｌからなる化合物が、下記式（３）で表される化合物である１〜３のいずれかに記載の有機薄膜太陽電池。

（式中、Ｒ^１〜Ｒ^７は、それぞれ水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基であり、
Ｒ^３及びＲ^４並びにＲ^５及びＲ^６は、それぞれ互いに結合して環構造を形成してもよい。
ｎは、０〜２の整数である）
５．前記１以上の電子供与性構造Ｄ及び１以上の電子受容性構造Ａを有するπ電子共役系分子骨格Ｌからなる化合物が、下記式（４）〜（７）のいずれかで表される化合物である１に記載の有機薄膜太陽電池。

（式中、Ａは、アルボニル基、又はジシアノエチレン基である。
Ｄ^１は、水素原子、置換若しくは無置換のアミノ基、又は置換若しくは無置換の水酸基である。
Ｄ^２は、ＮＲ^２であり、
Ｒ^２は、水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基である。
Ａｒは、それぞれ置換若しくは無置換のアリーレン基、又は置換若しくは無置換のヘテロアリーレン基である。
ｔ及びｕは、それぞれ０〜３の整数である。）
６．前記１以上の電子供与性構造Ｄ及び１以上の電子受容性構造Ａを有するπ電子共役系分子骨格Ｌからなる化合物が、下記式（８）で表される化合物である１に記載の有機薄膜太陽電池。

（式中、Ｄ^３〜Ｄ^１０は、それぞれ水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、置換若しくは無置換の炭素数６〜２０のアリール基、又は置換若しくは無置換のアミノ基であり、
Ｄ^３〜Ｄ^１０の少なくとも１つはジアリールアミノ基である。） According to the present invention, the following organic thin film solar cell is provided.
1. A pair of electrodes;
An organic solid multilayer part composed of one or more organic layers sandwiched between the pair of electrodes;
An organic thin-film solar cell in which an organic layer in contact with at least one of the pair of electrodes contains a compound containing a π-electron conjugated molecular skeleton L having one or more electron-donating structures D and one or more electron-accepting structures A.
2. 2. The organic thin film according to 1, wherein the compound comprising the π-electron conjugated molecular skeleton L having the one or more electron-donating structures D and the one or more electron-accepting structures A is a compound represented by the following formula (1): Solar cell.

(In formula, D is an electron-donating substituent.
A is an electron-accepting substituent.
Ar is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, respectively.
V is a substituted or unsubstituted vinylene group or a substituted or unsubstituted azomethine group, respectively.
p, q, and r are each an integer of 0-3.
D and Ar and V and A may be bonded to each other to form a ring structure. )
3. In the compound represented by the formula (1), Ar is a phenylene group, naphthalenyl group or anthracenylene group, V is a vinylene group, p, q and r are each an integer of 1 to 2, The group D is a substituted or unsubstituted hydroxyl group or a substituted or unsubstituted amino group, and the electron-accepting substituent A is a nitro group, a cyano group, or a substituent represented by the following formula (2) Organic thin film solar cell.

(Wherein X is an oxygen atom or NR ² ;
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
R is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, substituted or It is an unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 6 carbon atoms, or a substituted or unsubstituted arylamino group having 6 to 20 carbon atoms. )
4). Any one of 1 to 3, wherein the compound comprising the π-electron conjugated molecular skeleton L having the one or more electron-donating structures D and the one or more electron-accepting structures A is a compound represented by the following formula (3): The organic thin-film solar cell described in 1.

(Wherein R ^{1 to} R ⁷ are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
R ³ and R ⁴ and R ⁵ and R ⁶ may be bonded to each other to form a ring structure.
n is an integer of 0-2)
5. The compound comprising the π-electron conjugated molecular skeleton L having the one or more electron donating structures D and the one or more electron accepting structures A is a compound represented by any one of the following formulas (4) to (7). 2. The organic thin film solar cell according to 1.

(In the formula, A represents an alkenyl group or a dicyanoethylene group.
D ¹ is a hydrogen atom, a substituted or unsubstituted amino group, or a substituted or unsubstituted hydroxyl group.
D ² is NR ²
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
Ar is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, respectively.
t and u are each an integer of 0 to 3. )
6). 2. The organic thin film according to 1, wherein the compound comprising the π-electron conjugated molecular skeleton L having the one or more electron donating structures D and the one or more electron accepting structures A is a compound represented by the following formula (8): Solar cell.

(Wherein D ^{3 to} D ¹⁰ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted amino group, respectively. Group,
At least one of D ^{3 to} D ¹⁰ is a diarylamino group. )

  ADVANTAGE OF THE INVENTION According to this invention, it has the outstanding photoelectric conversion efficiency and can provide the organic thin film solar cell with few changes with time of a battery characteristic.

It is a schematic sectional drawing which shows one Embodiment of the organic thin film solar cell of this invention.

  The organic thin-film solar cell of the present invention has a pair of electrodes and an organic solid multilayer part composed of one or more organic layers sandwiched between the pair of electrodes, and the organic layer in contact with at least one of the pair of electrodes is 1 It contains a compound comprising a π-electron conjugated molecular skeleton L having the above electron donating structure D and one or more electron accepting structures A.

  A compound in which an organic layer in contact with at least one of a pair of electrodes includes a π-electron conjugated molecular skeleton L having one or more electron-donating structures D and one or more electron-accepting structures A (hereinafter simply referred to as a compound of the present invention) In some cases, the charge extraction efficiency from the electrode can be improved, and the photoelectric conversion efficiency of the organic thin-film solar cell can be improved.

  Examples of the electron donating structure D of the compound of the present invention include a substituted or unsubstituted hydroxyl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted alkyl group.

  Examples of the electron accepting structure A include a cyano group, a formyl group, a carbonyl group, an imino group, an arylcarbonyl group, an alkoxycarbonyl group, a carbamoyl group, a nitro group, an oxo group (═O), and a halogen atom.

  Examples of the π-electron conjugated molecular skeleton L include a benzene skeleton, a naphthalene skeleton, an anthranilic acid skeleton, a styrene skeleton, an ethylene skeleton, a stilbene skeleton, and a distyrylbenzene skeleton.

  The compound of the present invention is preferably any one of compounds represented by the following formulas (1) and (3) to (8). Preferred compounds of the present invention are described below.

（式中、Ｄは、電子供与性置換基である。
Ａは、電子受容性置換基である。
Ａｒは、それぞれ置換若しくは無置換のアリーレン基、又は置換若しくは無置換のヘテロアリーレン基である。
Ｖは、それぞれ置換若しくは無置換のビニレン基（−Ｃ＝Ｃ−）、又は置換若しくは無置換のアゾメチン基（−Ｃ＝Ｎ−）である。
ｐ、ｑ及びｒは、それぞれ０〜３の整数である。
Ｄ及びＡｒ並びにＶ及びＡは、それぞれ互いに結合して環構造を形成してもよい。） The compound of the present invention is preferably a compound represented by the following formula (1).

(In formula, D is an electron-donating substituent.
A is an electron-accepting substituent.
Ar is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, respectively.
V is a substituted or unsubstituted vinylene group (—C═C—) or a substituted or unsubstituted azomethine group (—C═N—), respectively.
p, q, and r are each an integer of 0-3.
D and Ar and V and A may be bonded to each other to form a ring structure. )

（式中、Ｘは、酸素原子、又はＮＲ^２であり、
Ｒ^２は、水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基である。
Ｒは、水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、置換若しくは無置換の炭素数１〜２０のアリール基、置換若しくは無置換の炭素数１〜６のアルコキシ基、置換若しくは無置換の炭素数６〜２０のアリールオキシ基、置換若しくは無置換の炭素数１〜６のアルキルアミノ基、又は置換若しくは無置換の炭素数６〜２０のアリールアミノ基である。） More preferably, in the compound represented by the formula (1), Ar is a phenylene group, a naphthalenyl group or an anthracenylene group, V is a vinylene group, p, q and r are each an integer of 1 to 2, The donating substituent D is a substituted or unsubstituted hydroxyl group or a substituted or unsubstituted amino group, and the electron-accepting substituent A is a nitro group, a cyano group, or a substituent represented by the following formula (2). .

(Wherein X is an oxygen atom or NR ² ;
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
R is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, substituted or It is an unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 6 carbon atoms, or a substituted or unsubstituted arylamino group having 6 to 20 carbon atoms. )

（式中、Ｒ^１〜Ｒ^７は、それぞれ水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基であり、
Ｒ^３及びＲ^４並びにＲ^５及びＲ^６は、それぞれ互いに結合して環構造を形成してもよい。
ｎは、０から２の整数である） The compound of the present invention is preferably a compound represented by the following formula (3).

(Wherein R ^{1 to} R ⁷ are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
R ³ and R ⁴ and R ⁵ and R ⁶ may be bonded to each other to form a ring structure.
n is an integer from 0 to 2)

（式中、Ａは、カルボニル基（Ｃ＝Ｏ）、又はジシアノエチレン基（Ｃ＝Ｃ（ＣＮ）_２）である。
Ｄ^１は、水素原子、置換若しくは無置換のアミノ基、又は置換若しくは無置換の水酸基である。
Ｄ^２は、ＮＲ^２であり、
Ｒ^２は、水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基である。
Ａｒは、それぞれ置換若しくは無置換のアリーレン基、又は置換若しくは無置換のヘテロアリーレン基である。
ｔ及びｕは、それぞれ０〜３の整数である。） The compound of the present invention is preferably a compound represented by any of the following formulas (4) to (7).

(In the formula, A represents a carbonyl group (C═O) or a dicyanoethylene group (C═C (CN) ₂ )).
D ¹ is a hydrogen atom, a substituted or unsubstituted amino group, or a substituted or unsubstituted hydroxyl group.
D ² is NR ²
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
Ar is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, respectively.
t and u are each an integer of 0 to 3. )

（式中、Ｄ^３〜Ｄ^１０は、それぞれ水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、置換若しくは無置換の炭素数６〜２０のアリール基、又は置換若しくは無置換のアミノ基であり、Ｄ^３〜Ｄ^１０の少なくとも１つはジアリールアミノ基である。） The compound of the present invention is preferably a compound represented by the following formula (8).

(Wherein D ^{3 to} D ¹⁰ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted amino group, respectively. And at least one of D ^{3 to} D ¹⁰ is a diarylamino group.)

Specific examples of the compound of the present invention are shown below.

（式中、Ｄは、それぞれ水素原子、置換若しくは無置換の炭素数１〜６のアルキル基、置換若しくは無置換の炭素数６〜２０のアリール基、又は置換若しくは無置換のアミノ基であり、互いに隣接するＤ同士が環を形成してもよい。
但し、Ｄが全て水素原子の場合を含まない。） As the compound of the present invention, the following quinone dyes (quinoid coloring system) and quinone dyes (quinoimine coloring system) can also be used.

(Wherein D is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted amino group, Ds adjacent to each other may form a ring.
However, the case where D is all hydrogen atoms is not included. )

Specific examples of the quinone colorant (quinoid color development system) and the quinone colorant (quinoimine color development system) which are the compounds of the present invention are as follows.

The cell structure of the organic thin-film solar battery of the present invention is not particularly limited as long as it has a structure having an organic solid multilayer part composed of one or more organic layers between a pair of electrodes. Specific examples of the cell structure include a structure having any one of the following configurations (1) to (8) on a stable insulating substrate.
In the following structures (1) to (8), for example, the buffer layer corresponds to an organic layer containing the compound of the present invention.

(1) Lower electrode / organic compound layer / buffer layer / upper electrode (2) Lower electrode / buffer layer / organic compound layer / upper electrode (3) Lower electrode / p layer / n layer / buffer layer / upper electrode (4) Lower electrode / buffer layer / p layer / n layer / upper electrode (5) lower electrode / buffer layer / p layer / n layer / buffer layer / upper electrode (6) lower electrode / p layer / i layer (or p material and n material mixed layer) / n layer / buffer layer / upper electrode (7) lower electrode / buffer layer / p layer / i layer (or mixed layer of p material and n material) / n layer / upper electrode (8) lower part Electrode / buffer layer / p layer / i layer (or mixed layer of p and n materials) / n layer buffer layer / upper electrode

FIG. 1: is a schematic sectional drawing which shows one Embodiment of the organic thin-film solar cell of this invention which has the structure of (1) among the said structures.
As shown in FIG. 1, the organic thin film solar cell 1 having the configuration (1) has a structure in which an upper electrode 10, a buffer layer 20, an organic compound layer 30, and a lower electrode 40 are stacked in this order.
In the organic thin film solar cell 1, a pair of electrodes (upper electrode 10 and lower electrode 40) sandwich an organic solid layer portion 50 composed of a buffer layer 20 and an organic compound layer 30. For example, the buffer layer in contact with the upper electrode 10 is the present invention. Containing the compound.

  The organic layer containing the compound of the present invention may be a layer in contact with at least one of the pair of electrodes, and is preferably a buffer layer.

  The organic layer may be a layer substantially composed of the compound of the present invention, or may be a mixed layer composed of the compound of the present invention and other components. As the other component, a known material of the organic layer can be used. For example, when the buffer layer contains the compound of the present invention, examples of other components include materials known as buffer layer materials.

  The organic thin film solar cell of this invention can use the well-known member and material used with an organic thin film solar cell. Hereinafter, the constituent members of each layer will be described.

[Buffer layer]
Since organic thin film solar cells generally have a small total film thickness, the upper electrode and the lower electrode are short-circuited, which may reduce the yield of cell fabrication. The short circuit can be prevented by stacking buffer layers.
The buffer layer may be a laminate of two or more layers, but when the buffer layer contains the compound of the present invention, the buffer layer in contact with the electrode contains the compound of the present invention.

Examples of the material for the buffer layer include compounds having sufficiently high carrier mobility so that the short-circuit current does not decrease even when the film thickness is increased. For example, if it is a low molecular compound, the aromatic cyclic acid anhydride represented by NTCDA shown below etc. will be mentioned, and if it is a high molecular compound, poly (3,4-ethylenedioxy) thiophene: polystyrene sulfonate (PEDOT: PSS), polyaniline: camphorsulfonic acid (PANI: CSA), and other known conductive polymers.

Moreover, as a material of a buffer layer, the well-known material for positive hole barrier layers, the material for electron barrier layers, etc. are mentioned for an organic EL element use, for example. A preferable material for the hole blocking layer is a compound having a sufficiently large ionization potential, and a preferable material for the electron blocking layer is a compound having a sufficiently small electron affinity.
Specifically, bathocuproin (BCP), bathophenanthroline (BPhen), and the like, which are well-known materials for organic EL applications, can be used as the cathode-side hole barrier layer material.

In addition to the above compounds, an inorganic semiconductor compound that is an n-layer material described later may be used as a material for the buffer layer, and CdTe, p-Si, SiC, GaAs, WO _{3 and the} like, which are p-type inorganic semiconductor compounds, may be used. It can also be used.

[Organic layer]
The organic layer includes a p layer, a mixed layer (i layer) of p material and n material, and an n layer.
The material of the p layer (p material) and the material of the n layer (n material) are not particularly limited, and known compounds used for organic thin film solar cells can be used.

When the p material is an organic compound, the p material is preferably an organic compound that functions as a hole acceptor.
Examples of the organic compound of the p material include N, N′-bis (3-tolyl) -N, N′-diphenylbenzidine (mTPD), N, N′-dinaphthyl-N, N′-diphenylbenzidine (NPD). , 4,4 ′, 4 ″ -tris (phenyl-3-tolylamino) triphenylamine (MTDATA) and other amine compounds, phthalocyanine (Pc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), titanyl Examples include phthalocyanines such as phthalocyanine (TiOPc), porphyrins represented by octaethylporphyrin (OEP), platinum octaethylporphyrin (PtOEP), zinc tetraphenylporphyrin (ZnTPP), and the like.

  When the p material is a polymer compound, examples of the polymer compound include main chain conjugated polymers such as polyhexylthiophene (P3HT) and methoxyethylhexyloxyphenylene vinylene (MEHPPV), and polyvinylcarbazole. Examples include side chain polymers.

The n material is preferably an organic compound having a function as an electron acceptor.
Examples of the organic compound of the n material include, for example, fullerene derivatives such as C ₆₀ and C ₇₀ , carbon nanotubes, perylene derivatives, polycyclic quinones, quinacridones, and the like in the polymer system CN-poly (phenylene-vinylene), MEH-CN- PPV, —CN group or CF ₃ group-containing polymer, poly (fluorene) derivative and the like can be mentioned.

  The organic compound that functions as an electron acceptor is preferably a material having a high electron mobility or a material having a low electron affinity. A sufficient open-circuit voltage can be realized by using a material having a low electron affinity for the n-layer.

An n-type inorganic semiconductor compound can also be used for the n layer.
Examples of the n-type inorganic semiconductor compound include doping semiconductors and compound semiconductors such as n-Si, GaAs, CdS, PbS, CdSe, InP, Nb ₂ O ₅ , WO ₃ , Fe ₂ O ₃ , and titanium dioxide (TiO 2). ₂ ), titanium oxide such as titanium monoxide (TiO) and dititanium trioxide (Ti ₂ O ₃ ), and conductive oxides such as zinc oxide (ZnO) and tin oxide (SnO ₂ ).
The n-type characteristic inorganic semiconductor compound may be used alone or in combination of two or more, preferably titanium oxide, particularly preferably titanium dioxide.

  The i layer can be formed by mixing the material of the p layer and the material of the n layer.

[electrode]
The pair of electrodes (upper electrode and lower electrode) of the organic thin film solar cell of the present invention is not particularly limited as long as it is a thin film having electrical conductivity in the dark field.

An electrode made of a known conductive material can be used for the upper electrode and the lower electrode.
As an electrode connected to the p layer, for example, an electrode made of a metal such as tin-doped indium oxide (ITO), gold (Au), osmium (Os), palladium (Pd), or the like can be used.
As the counter electrode connected to the p layer, for example, an electrode made of a metal such as silver (Ag), aluminum (Al), indium (In), calcium (Ca), platinum (Pt) lithium (Li), Mg: An electrode made of a binary metal such as Ag, Mg: In or Al: Li, and an electrode connected to the p layer can be used.

In order to obtain highly efficient photoelectric conversion characteristics, it is desirable that at least one electrode of the organic thin-film solar cell be sufficiently transparent in the sunlight spectrum. The light transmittance of the transparent electrode is desirably 10% or more. The transparent electrode can be formed by using a known conductive material so as to ensure a predetermined translucency by a method such as vapor deposition or sputtering.
In the pair of electrodes, it is preferable that one of the electrodes includes a metal having a high work function and the other includes a metal having a low work function.

[substrate]
The substrate is preferably a substrate having mechanical and thermal strength and transparency, and examples thereof include a glass substrate and a transparent resin film.
Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide and the like can be mentioned.

[Formation method]
The formation of each layer of the organic thin film solar cell of the present invention is performed by a dry film formation method such as vacuum deposition, sputtering, plasma, ion plating, or wet film formation such as spin coating, dip coating, casting, roll coating, flow coating, and ink jet. The law can be applied.

  In the case of the dry film forming method, a known resistance heating method is preferable, and for forming the mixed layer, for example, a film forming method by simultaneous vapor deposition from a plurality of evaporation sources is preferable. More preferably, the substrate temperature is controlled during film formation.

In the case of a wet film forming method, a material for forming each layer is dissolved or dispersed in an appropriate solvent to prepare a light-emitting organic solution to form a thin film, and any solvent can be used.
Examples of the solvent include halogen-based hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene, and ether-based solvents such as dibutyl ether, tetrahydrofuran, dioxane, and anisole. Solvent, alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, carbonization such as benzene, toluene, xylene, ethylbenzene, hexane, octane, decane, tetralin, etc. Examples thereof include hydrogen solvents, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate. Of these, hydrocarbon solvents or ether solvents are preferable. These solvents may be used alone or in combination.
In addition, the solvent which can be used is not limited to these.

The thickness of each layer is not particularly limited, but is set to an appropriate thickness.
In general, it is known that the exciton diffusion length of an organic thin film is short, and if the film thickness is too thick, the exciton is deactivated before reaching the heterointerface, which may reduce the photoelectric conversion efficiency. On the other hand, if the film thickness is too thin, pinholes and the like are generated, so that sufficient diode characteristics cannot be obtained, and conversion efficiency may be reduced. The film thickness of each normal layer is suitably in the range of 1 nm to 10 μm, but more preferably in the range of 5 nm to 0.2 μm.

In the present invention, an appropriate resin or additive may be used for the organic layer of the organic thin film solar cell in order to improve the film formability and prevent pinholes in the film.
Usable resins include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose and other insulating resins and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.
Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.

  Hereinafter, examples of the present invention will be described in detail, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 0.7 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. Mount the glass substrate with the transparent electrode line after cleaning on the substrate holder of the vacuum evaporation system, and heat-deposit copper phthalocyanine on the surface where the transparent electrode line, which is the lower electrode, is formed to cover the transparent electrode. Then, a film was formed at 0.5 Å / s to form a p-layer having a thickness of 30 nm. Next, fullerene (C ₆₀ ) was deposited by resistance heating vapor deposition, and a film was formed at 0.5 Å / s to form an n layer having a film thickness of 60 nm on the p layer. The following compound 1 (manufactured by Dojin Chemical Co., Ltd.) is deposited by resistance heating, a buffer layer having a thickness of 10 nm is formed on the n layer, and metal Al is deposited on the buffer layer at a thickness of 100 nm as an upper electrode. A solar cell was produced. The area was 0.05 cm ² .

The IV characteristic was measured for the produced organic thin-film solar cell under AM1.5 conditions (incident intensity (Pin) 100 mW / cm ² ). Table 1 shows the open-circuit voltage (Voc ₀ ), short-circuit current density (Jsc ₀ ), fill factor (FF ₀ ), and photoelectric conversion efficiency (η ₀ ) of the organic thin-film solar cell, which are obtained results.
The photoelectric conversion efficiency was derived from the following formula.

The produced organic thin film solar cell was stored in a nitrogen atmosphere at 25 ° C. in a dark room for 30 days, and the IV characteristics (Voc ₃₀ , Jsc ₃₀ , FF ₃₀ and η ₃₀ ) of the organic thin film solar cell were measured again. The results are shown in Table 1.
In addition, the time performance (Voc ₃₀ , Jsc ₃₀ , FF ₃₀ and η ₃₀ ) and the initial performance (Voc ₀ , Jsc ₀ , FF ₀ and η ₀ ) ratio (time performance / initial performance) are also shown in Table 1. .

Example 2
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that the following compound 2 was used instead of the compound 1. The results are shown in Table 1.

Example 3
Organic thin-film solar cells were prepared and evaluated in the same manner as in Example 1 except that the following compound 3 (manufactured by Aldrich) was used instead of compound 1. The results are shown in Table 1.

Comparative Example 1
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that the buffer layer was not formed. The results are shown in Table 1.

Comparative Example 2
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that the following compound 4 (manufactured by Tokyo Chemical Industry) was used instead of compound 1. The results are shown in Table 1.

Comparative Example 3
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that the following compound 5 was used instead of compound 1. The results are shown in Table 1.

  From Table 1, it can be seen that the organic thin film solar cell of the present invention is excellent in photoelectric conversion efficiency and has little change with time in battery characteristics.

  The organic thin film solar cell of the present invention can be used as a power source for watches, mobile phones, mobile personal computers and the like.

DESCRIPTION OF SYMBOLS 1 Organic thin film solar cell 10 Upper electrode 20 Buffer layer 30 Organic compound layer 40 Lower electrode 50 Organic solid multilayer part

Claims (5)

A pair of electrodes;
Having an organic solid multilayer part sandwiched between the pair of electrodes,
The organic solid multilayer part includes a buffer layer and an organic compound layer,
The buffer layer is in contact with at least one of the pair of electrodes ;
The buffer layer includes one or more electron-donating substituents D 1 selected from a substituted or unsubstituted amino group , and one or more electron-accepting substituents A selected from a cyano group, a carbonyl group, and a dicyanoethylene group. An organic thin-film solar cell containing a compound containing a π-electron conjugated molecular skeleton L. The compound comprising the π-electron conjugated molecular skeleton L having the one or more electron-donating substituents D and one or more electron-accepting substituents A is a compound represented by the following formula (1): The organic thin film solar cell described.

(Wherein, D is a said electron-donating substituent D.
A is the electron-accepting substituent A.
Ar is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, respectively.
V is a substituted or unsubstituted vinylene group or a substituted or unsubstituted azomethine group, respectively.
r is an integer of 1 to 3.
p and q are each an integer of 0 to 3, but are not 0 at the same time .
D and Ar and V and A may be bonded to each other to form a ring structure. ) A compound comprising a π-electron conjugated molecular skeleton L having one or more electron-donating substituents D and one or more electron-accepting substituents A is represented by any of the following formulas (4) to (7). The organic thin-film solar cell according to claim 1, which is a compound.

(In the formula, A represents a carbonyl group or a dicyanoethylene group.
D ¹ is a hydrogen atom, a substituted or unsubstituted amino group, or Ri hydroxyl der substituted or unsubstituted, at least one of D ¹ is a substituted or unsubstituted amino group.
D ² is NR ²
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
Ar is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, respectively.
t and u are each an integer of 0 to 3. ) The compound comprising the π-electron conjugated molecular skeleton L having the one or more electron-donating substituents D and one or more electron-accepting substituents A is a compound represented by the following formula (8): The organic thin film solar cell described.

(Wherein D ^{3 to} D ¹⁰ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted amino group, respectively. Group,
At least one of D ^{3 to} D ¹⁰ is a diarylamino group. ) The organic compound layer, an organic thin film solar cell according to any one of claims 1-4 comprising a p-layer and the n layer.

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