JP2018018967A - Charge transporting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a charge transporting composition which can offer a thin film suitable for a hole-collecting layer of an organic photoelectric conversion device.SOLUTION: A charge transporting composition comprises: a charge-transporting substance including a phenothiazine derivative represented by the formula (1) or (2); and a solvent. (In the formula, Rto Rindependently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group with C1-20, a thioalkoxy group with C1-20, an alkyl group with C1-20, an alkenyl group with C2-20, an alkynyl group with C2-20, a haloalkyl group with C1-20, an aryl group with C6-20, an aralkyl group with C7-20, or an acyl group with C1-20; and Arand Arindependently represent an aromatic group, such as a phenyl group, a biphenyl group, or an anthryl group, which may be substituted.)SELECTED DRAWING: None

Description

  The present invention relates to a charge transporting composition, and more particularly to a charge transporting composition suitable for forming a hole collection layer of an organic photoelectric conversion element.

An organic solar cell is a solar cell element using an organic substance as an active layer or a charge transport material. A dye-sensitized solar cell developed by Gretzell; W. Organic thin-film solar cells developed by Tan are well known (Non-Patent Documents 1 and 2).
All are lightweight, thin film, flexible, roll-to-roll, and other features that are different from the current mainstream inorganic solar cells. Formation is expected.
In particular, organic thin-film solar cells (hereinafter sometimes abbreviated as OPV) have features such as electrolyte-free and heavy metal compound-free, and recently, a photoelectric conversion efficiency (hereinafter abbreviated as PCE) 10.6 by a group of UCLA et al. % Has attracted a great deal of attention for reasons such as non-patent literature 3).

On the other hand, the organic thin-film solar cell exhibits high photoelectric conversion efficiency even at low illuminance compared to a photoelectric conversion element using an existing silicon-based material, and can be thinned and pixels can be miniaturized. Due to the feature of being able to combine the properties of a color filter, it is attracting attention not only as a solar battery but also as an optical sensor such as an image sensor (Patent Documents 1 and 2 and Non-Patent Document 4). ). Hereinafter, the organic thin film solar cell is generically referred to as an organic photoelectric conversion element (hereinafter sometimes abbreviated as OPV) including applications such as an optical sensor.
The organic photoelectric conversion element includes an active layer (photoelectric conversion layer), a charge (hole, electron) collection layer, an electrode (anode, cathode), and the like.
Among these, the active layer and the charge collection layer are generally formed by a vacuum deposition method, but there are problems with the vacuum deposition method in terms of the complexity of the mass production process, the high cost of the apparatus, the utilization efficiency of the material, etc. There is.

From these points, water dispersible polymer organic conductive materials such as PEDOT / PSS may be used as a coating type material for the hole collection layer, but since it is an aqueous dispersion, it is completely free of moisture. There is a problem that it is difficult to control removal and re-absorption, and it is easy to accelerate the deterioration of the element.
Moreover, since the PEDOT / PSS aqueous dispersion has the property that solids are likely to aggregate, there are problems that coating film defects are likely to occur, clogging and corrosion of the coating apparatus are likely to occur, and heat resistance In terms of performance, it is insufficient, and various problems remain in mass production.

JP 2003-234460 A JP 2008-258474 A

Nature, vol.353, 737-740 (1991) Appl. Phys. Lett., Vol. 48, 183-185 (1986) Nature Photonics Vol.6, 153-161 (2012) Scientific Reports, Vol.5: 7708, 1-7 (2015)

  This invention is made | formed in view of the said situation, and it aims at providing the charge transportable composition which gives the thin film suitable for the hole collection layer of an organic photoelectric conversion element.

  As a result of intensive investigations to achieve the above object, the present inventors have shown that a predetermined phenothiazine derivative exhibits high hole transportability, and a thin film containing this is used as a hole collection layer of an OPV element. In some cases, it was found that an OPV element exhibiting good PCE at a high yield was obtained, and the present invention was completed.

（式（１）および（２）中、Ｒ¹〜Ｒ⁶は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のチオアルコキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または炭素数１〜２０のアシル基を表し、Ａｒ¹およびＡｒ²は、互いに独立して、置換されていてもよい、フェニル基、ビフェニル基、アントリル基、フェナントリル基、フルオレニル基、テルフェニル基、テトラセニル基、ペンタセニル基、ペリレニル基、チエニル基、フリル基、オキサゾリル基、チアゾリル基、イミダゾリル基、ピリジル基、ピリミジニル基、ピラジニル基、ピリダジニル基、ピラジル基、キノリル基、キノキサリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、およびベンゾイミダゾリル基から選ばれる芳香族基を表す。）
２． 前記式（１）および（２）中のＡｒ¹およびＡｒ²が、互いに独立して、式（３）で表される基である１の電荷輸送性組成物、

（式中、Ａｒ³およびＡｒ⁴は、互いに独立して、水素原子、またはアミノ基、フェニルアミノ基、ジフェニルアミノ基、アルコキシ基、アルキルチオ基もしくはアルキル基で置換されていてもよい芳香族基を表し、この芳香族基は、フェニル基、ビフェニル基、アントリル基、フェナントリル基、フルオレニル基、テルフェニル基、テトラセニル基、ペンタセニル基、ペリレニル基、チエニル基、フリル基、オキサゾリル基、チアゾリル基、イミダゾリル基、ピリジル基、ピリミジニル基、ピラジニル基、ピリダジニル基、ピラジル基、キノリル基、キノキサリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、およびベンゾイミダゾリル基から選ばれる基を表す。ただし、Ａｒ³およびＡｒ⁴が同時に水素原子となることはなく、また、Ａｒ³およびＡｒ⁴がともに芳香族基の場合、それらは互いに単結合で結合していても、ヘテロ原子を介して結合していてもよい。
Ｒ⁷〜Ｒ¹⁰は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のチオアルコキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または炭素数１〜２０のアシル基を表す。）
３． 前記式（３）で表される基が、式（４）〜（６）で表されるいずれかの基である１の電荷輸送性組成物、

（式中、Ｒ⁷〜Ｒ³³は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のチオアルコキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または炭素数１〜２０のアシル基を表す。）
４． 前記電荷輸送性物質が、式（７）で表されるフェノチアジン誘導体である１の電荷輸送性組成物、

｛式中、Ｒ¹〜Ｒ¹⁰は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のチオアルコキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または炭素数１〜２０のアシル基を表し、Ｘ¹およびＸ²は、水素原子、式（８）で表される基、式（９）で表される基または式（１０）で表される基を表す。

（式中、Ｒ¹¹〜Ｒ³³は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のチオアルコキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または炭素数１〜２０のアシル基を表す。）｝
５． 前記Ｘ¹およびＸ²が、式（８）で表される基または式（９）で表される基である４の電荷輸送性組成物、
６． 前記Ｒ¹〜Ｒ³³が、水素原子である４または５の電荷輸送性組成物、
７． さらに、電子受容性ドーパント物質を含む１〜６のいずれかの電荷輸送性組成物、
８． 前記電子受容性ドーパント物質が、式（Ｄ１）で表されるアリールスルホン酸化合物である７の電荷輸送性組成物、

（式中、Ｘは、Ｏを表し、Ａは、ナフタレン環またはアントラセン環を表し、Ｂは、２〜４価のパーフルオロビフェニル基を表し、ｌは、Ａに結合するスルホン酸基数を表し、１≦ｌ≦４を満たす整数であり、ｑは、ＢとＸとの結合数を示し、２〜４を満たす整数である。）
９． 有機光電変換素子の正孔捕集層用である１〜８のいずれかの電荷輸送性組成物、
１０． 前記有機光電変換素子が、有機薄膜太陽電池または光センサーである９の電荷輸送性組成物、
１１． ９または１０の電荷輸送性組成物を用いてなる有機光電変換素子の正孔捕集層、
１２． １１の正孔捕集層と、それに接するように設けられた活性層とを有する有機光電変換素子、
１３． 前記活性層が、フラーレン誘導体を含む１２の有機光電変換素子、
１４． 前記活性層が、主鎖にチオフェン骨格を含むポリマーを含む１２の有機光電変換素子、
１５． 前記活性層が、フラーレン誘導体および主鎖にチオフェン骨格を含むポリマーを含む１２の有機光電変換素子、
１６． 有機薄膜太陽電池または光センサーである１２〜１５のいずれかの有機光電変換素子、
１７． 式（１）または式（２）で表されることを特徴とするフェノチアジン誘導体、

（式（１）および（２）中、Ｒ¹〜Ｒ⁶は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のチオアルコキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または炭素数１〜２０のアシル基を表し、Ａｒ¹およびＡｒ²は、互いに独立して、置換フェニル基、置換されていてもよい、ビフェニル基、アントリル基、フェナントリル基、フルオレニル基、テルフェニル基、テトラセニル基、ペンタセニル基、ペリレニル基、チエニル基、フリル基、オキサゾリル基、チアゾリル基、イミダゾリル基、ピリジル基、ピリミジニル基、ピラジニル基、ピリダジニル基、ピラジル基、キノリル基、キノキサリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、およびベンゾイミダゾリル基から選ばれる芳香族基を表す。）
１８． 前記式（１）および（２）中のＡｒ¹およびＡｒ²が、互いに独立して、式（３）で表される基である１７のフェノチアジン誘導体、

（式中、Ａｒ³およびＡｒ⁴は、互いに独立して、水素原子、またはアミノ基、フェニルアミノ基、ジフェニルアミノ基、トリフェニルアミノ基、アルコキシ基、アルキルチオ基もしくはアルキル基で置換されていてもよい芳香族基を表し、この芳香族基は、フェニル基、ビフェニル基、アントリル基、フェナントリル基、フルオレニル基、テルフェニル基、テトラセニル基、ペンタセニル基、ペリレニル基、チエニル基、フリル基、オキサゾリル基、チアゾリル基、イミダゾリル基、ピリジル基、ピリミジニル基、ピラジニル基、ピリダジニル基、ピラジル基、キノリル基、キノキサリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、およびベンゾイミダゾリル基から選ばれる基を表す。ただし、Ａｒ³およびＡｒ⁴が同時に水素原子となることはなく、また、Ａｒ³およびＡｒ⁴がともに芳香族基の場合、それらは互いに単結合で結合していても、ヘテロ原子を介して結合していてもよい。Ｒ⁷〜Ｒ¹⁰は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のチオアルコキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または炭素数１〜２０のアシル基を表す。）
１９． 前記式（３）で表される基が、式（４）〜（６）で表されるいずれかの基である１８のフェノチアジン誘導体、

（式中、Ｒ⁷〜Ｒ³³は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のチオアルコキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または炭素数１〜２０のアシル基を表す。）
２０． 式（７）で表される１７のフェノチアジン誘導体、

｛式中、Ｒ¹〜Ｒ¹⁰は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のチオアルコキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または炭素数１〜２０のアシル基を表し、Ｘ¹およびＸ²は、式（８）で表される基、式（９）で表される基または式（１０）で表される基を表す。

（式中、Ｒ¹¹〜Ｒ³³は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のチオアルコキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または炭素数１〜２０のアシル基を表す。）｝
２１． 式（１１）または（１２）で表される１７のフェノチアジン誘導体

を提供する。 That is, the present invention
1. A charge transporting composition comprising a charge transporting material comprising a phenothiazine derivative represented by formula (1) or formula (2) and a solvent;

(In Formula (1) and (2), R < ¹ > -R < ⁶ > is mutually independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C1-C20 alkoxy group, a C1-C20 Thioalkoxy group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon A phenyl group, a biphenyl group, an anthryl group, a phenanthryl group, which represents an aralkyl group of 7 to 20 or an acyl group of 1 to 20 carbon atoms, and Ar ¹ and Ar ² are each independently substituted. , Fluorenyl group, terphenyl group, tetracenyl group, pentacenyl group, perylenyl group, thienyl group, furyl group, oxazolyl group, thiazolyl group, imidazolyl group, pyridyl group, pyrimidinyl , Pyrazinyl group, pyridazinyl group, a pyrazinyl group, quinolyl group, quinoxalyl group, benzoxazolyl group, an aromatic group selected from benzothiazolyl group and a benzimidazolyl group.)
2. 1 charge transportable composition wherein Ar ¹ and Ar ^{2 in the} formulas (1) and (2) are each independently a group represented by the formula (3);

(In the formula, Ar ³ and Ar ⁴ are each independently a hydrogen atom or an aromatic group optionally substituted with an amino group, a phenylamino group, a diphenylamino group, an alkoxy group, an alkylthio group or an alkyl group. This aromatic group is a phenyl group, biphenyl group, anthryl group, phenanthryl group, fluorenyl group, terphenyl group, tetracenyl group, pentacenyl group, perylenyl group, thienyl group, furyl group, oxazolyl group, thiazolyl group, imidazolyl group , Pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, pyrazyl group, quinolyl group, quinoxalyl group, benzoxazolyl group, benzothiazolyl group, and benzoimidazolyl group, provided that Ar ³ and Ar ⁴ are simultaneously selected. Never become a hydrogen atom, For r ³ and Ar ⁴ are both aromatic groups, even if they are bound by a single bond to each other may be bonded through a hetero atom.
R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. Group, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, or carbon number 1 to 20 acyl groups are represented. )
3. 1 charge transportable composition, wherein the group represented by the formula (3) is any group represented by the formulas (4) to (6);

(In the formula, R ^{7 to} R ³³ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms.)
4). 1 charge transporting composition, wherein the charge transporting material is a phenothiazine derivative represented by the formula (7):

{In the formula, R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms, and X ¹ and X ² are each represented by a hydrogen atom, a group represented by formula (8), a group represented by formula (9), or formula (10). Represents a group.

(In the formula, R ^{11 to} R ³³ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms.)}
5). The charge transporting composition of 4, wherein X ¹ and X ² are a group represented by the formula (8) or a group represented by the formula (9):
6). 4 or 5 charge transporting compositions, wherein R ^{1 to} R ³³ are hydrogen atoms;
7). Furthermore, the charge transporting composition according to any one of 1 to 6, comprising an electron-accepting dopant substance,
8). The charge transporting composition according to 7, wherein the electron-accepting dopant material is an aryl sulfonic acid compound represented by the formula (D1):

(In the formula, X represents O, A represents a naphthalene ring or an anthracene ring, B represents a divalent to tetravalent perfluorobiphenyl group, and l represents the number of sulfonic acid groups bonded to A. (It is an integer satisfying 1 ≦ l ≦ 4, and q represents the number of bonds between B and X, and is an integer satisfying 2 to 4.)
9. The charge transporting composition according to any one of 1 to 8, which is used for a hole collection layer of an organic photoelectric conversion device,
10. 9. The charge transporting composition according to 9, wherein the organic photoelectric conversion element is an organic thin film solar cell or an optical sensor,
11. A hole collection layer of an organic photoelectric conversion device comprising the charge transporting composition of 9 or 10;
12 An organic photoelectric conversion element having 11 hole collection layers and an active layer provided in contact therewith,
13. 12 organic photoelectric conversion elements in which the active layer contains a fullerene derivative;
14 12 organic photoelectric conversion elements in which the active layer contains a polymer containing a thiophene skeleton in the main chain;
15. 12 organic photoelectric conversion elements in which the active layer contains a fullerene derivative and a polymer containing a thiophene skeleton in the main chain;
16. Any one of organic photoelectric conversion elements of 12 to 15, which are organic thin-film solar cells or optical sensors;
17. A phenothiazine derivative represented by the formula (1) or (2):

(In Formula (1) and (2), R < ¹ > -R < ⁶ > is mutually independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C1-C20 alkoxy group, a C1-C20 Thioalkoxy group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon Represents an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms, and Ar ¹ and Ar ² are each independently a substituted phenyl group, an optionally substituted biphenyl group, an anthryl group, or phenanthryl. Group, fluorenyl group, terphenyl group, tetracenyl group, pentacenyl group, perylenyl group, thienyl group, furyl group, oxazolyl group, thiazolyl group, imidazolyl group, pyridyl group, pyrimidide Group, represents a pyrazinyl group, pyridazinyl group, pyrazinyl group, quinolyl group, quinoxalyl group, benzoxazolyl group, an aromatic group selected from benzothiazolyl group and a benzimidazolyl group.)
18. 17 phenothiazine derivatives wherein Ar ¹ and Ar ^{2 in the} formulas (1) and (2) are each independently a group represented by the formula (3);

(In the formula, Ar ³ and Ar ⁴ may be independently of each other a hydrogen atom or an amino group, a phenylamino group, a diphenylamino group, a triphenylamino group, an alkoxy group, an alkylthio group or an alkyl group. Represents a good aromatic group, and this aromatic group includes a phenyl group, a biphenyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a terphenyl group, a tetracenyl group, a pentacenyl group, a perylenyl group, a thienyl group, a furyl group, an oxazolyl group, thiazolyl group, an imidazolyl group, a pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, pyrazinyl group, quinolyl group, a quinoxalyl group, benzoxazolyl group, benzothiazolyl group a group selected from and benzimidazolyl group. However, Ar ³ and Ar ⁴ is a hydrogen atom at the same time Not Rukoto, also when both the aromatic groups Ar ³ and Ar ⁴ is, even if they are linked by a single bond to each other, good .R ⁷ to R ¹⁰ may be bonded through a hetero atom Independently of each other, a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and 2 to 2 carbon atoms 20 alkenyl groups, alkynyl groups having 2 to 20 carbon atoms, haloalkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or acyl groups having 1 to 20 carbon atoms Represents.)
19. 18 phenothiazine derivatives, wherein the group represented by the formula (3) is any group represented by the formulas (4) to (6);

(In the formula, R ^{7 to} R ³³ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms.)
20. 17 phenothiazine derivatives represented by formula (7),

{In the formula, R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms, and X ¹ and X ² are a group represented by the formula (8), a group represented by the formula (9), or a group represented by the formula (10). Represent.

(In the formula, R ^{11 to} R ³³ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms.)}
21. 17 phenothiazine derivatives represented by the formula (11) or (12)

I will provide a.

  The charge transporting composition of the present invention can be produced using a charge transporting substance composed of a phenothiazine derivative that can be easily synthesized by a known method, and a thin film obtained therefrom can be used as a hole collection layer. In addition, an organic thin film solar cell having a good PCE can be obtained. In addition, since a highly uniform thin film can be formed by using the charge transporting composition of the present invention, current leakage can be suppressed and the reverse bias dark current can be reduced by using the highly uniform thin film as a hole collection layer. Can be suppressed. Therefore, the thin film made of the charge transporting composition of the present invention can be applied to an element structure similar to that of an organic thin film solar cell, and a small number of photons can be detected by being converted into electrons. The obtained hole collection layer can be applied to optical sensor applications such as high-performance image sensor applications.

Hereinafter, the present invention will be described in more detail.
The charge transporting composition of the present invention includes a charge transporting material composed of a phenothiazine derivative represented by the formula (1) or (2) and a solvent.
In the present invention, charge transportability is synonymous with conductivity and is synonymous with hole transportability. The charge transporting substance may be a substance having a charge transporting property per se, or a substance having a charge transporting property when used together with an electron accepting substance. In addition, the charge transporting composition may be a charge transporting composition itself, or the solid film obtained thereby may have a charge transporting function.

In formulas (1) and (2), R ^{1 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, or a thio having 1 to 20 carbon atoms. Alkoxy group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon number Represents an aralkyl group having 7 to 20 carbon atoms or an acyl group having 1 to 20 carbon atoms, and Ar ¹ and Ar ² are each independently a phenyl group, a biphenyl group, an anthryl group, a phenanthryl group, Fluorenyl group, terphenyl group, tetracenyl group, pentacenyl group, perylenyl group, thienyl group, furyl group, oxazolyl group, thiazolyl group, imidazolyl group, pyridyl group, pyrimidinyl group Pyrazinyl group, pyridazinyl group, a pyrazinyl group, quinolyl group, quinoxalyl group, benzoxazolyl group, an aromatic group selected from benzothiazolyl group and a benzimidazolyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, c-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosa Nyloxy group etc. are mentioned.

Specific examples of the thioalkoxy group having 1 to 20 carbon atoms include groups in which the oxygen atom of the alkoxy group is substituted with a sulfur atom.
Specific examples of the thioalkoxy (alkylthio) group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, s-butylthio group, t-butylthio group. Group, n-pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetra Examples include decylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, n-octadecylthio group, n-nonadecylthio group, n-eicosanylthio group and the like.

  Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and n-pentyl group. A chain alkyl group having 1 to 20 carbon atoms such as n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group , Cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, bicyclodecyl group, etc. Examples thereof include a cyclic alkyl group.

  Specific examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n- Examples include 1-pentenyl group, n-1-decenyl group, n-1-eicocenyl group and the like.

  Specific examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, and n-3-butynyl. Group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4-pentynyl group, 1-methyl-n-butynyl group, 2- Methyl-n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n-1-decynyl group, n-1-pentadecynyl group, n- 1-eicosinyl group etc. are mentioned.

Examples of the haloalkyl group having 1 to 20 carbon atoms include groups in which at least one hydrogen atom in the alkyl group is substituted with a halogen atom. The halogen atom may be any of chlorine, bromine, iodine and fluorine atoms. Of these, a fluoroalkyl group is preferable, and a perfluoroalkyl group is more preferable.
Specific examples thereof include fluoromethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 2,2,3,3,3- Pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, nonafluorobutyl group, 4,4,4-trifluoro Butyl group, undecafluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoro Pentyl group, tridecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 2,2,3,3,4,4,5 , 5,6,6-Decafluo Hexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, and the like.

  Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group. Group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.

Specific examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group, p-ethylphenylmethyl. Group, 2-propylphenylmethyl group, 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, α-naphthylmethyl group and the like.
Specific examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.

In the above formulas (1) and (2), Ar ¹ and Ar ² are ^one kind selected from a predetermined aromatic group which may be substituted, and examples of the substituent include an amino group, a phenylamino group, and diphenyl. Examples thereof include an amino group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a phenothiazin-10-yl group, and a carbazol-9-yl group. At least a part of the hydrogen atoms of the benzene ring contained in the group may be further substituted with an amino group, a phenylamino group, or a diphenylamino group.
Among these, Ar ¹ and Ar ² include a phenyl group, a phenyl group substituted with a diphenylamino group, a phenyl group substituted with phenothiazin-10-yl, and a phenyl group substituted with a carbazol-9-yl group. preferable. In addition, as for the substitution position of the substituent on these phenyl groups, para position is preferable with respect to the amino group interposed between phenothiazine rings.
Particularly preferred examples of Ar ¹ and Ar ² include a group represented by the following formula (3).

In the formula (3), Ar ³ and Ar ⁴ are each independently a hydrogen atom, or an aromatic group that may be substituted with an amino group, a phenylamino group, a diphenylamino group, an alkoxy group, an alkylthio group, or an alkyl group. This aromatic group is a phenyl group, biphenyl group, anthryl group, phenanthryl group, fluorenyl group, terphenyl group, tetracenyl group, pentacenyl group, perylenyl group, thienyl group, furyl group, oxazolyl group, thiazolyl group, It represents a group selected from an imidazolyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a pyrazyl group, a quinolyl group, a quinoxalyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group.
However, Ar ³ and Ar ⁴ are not simultaneously hydrogen atoms, and when Ar ³ and Ar ⁴ are both aromatic groups, they are bonded via a heteroatom even though they are bonded to each other by a single bond. You may do it. Examples of the bond through a hetero atom include —O—, —S—, —NH— and the like. In the present invention, Ar ³ and Ar ⁴ are more preferably bonded by a single bond or -S-.
Among these, as Ar ³ and Ar ⁴ , one is a phenyl group and the other is a hydrogen atom, and simultaneously a phenyl group, a group in which two phenyl groups are bonded by a single bond (including a nitrogen atom, a carbazol-9-yl group A group in which two phenyl groups are bonded by -S- (including a nitrogen atom and a phenothiazin-10-yl group) is preferable.

On the other hand, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. An alkyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or Represents an acyl group having 1 to 20 carbon atoms, and specific examples of these alkoxy groups, thioalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, aryl groups, aralkyl groups, and acyl groups are the same as described above. Is mentioned.
Among these, R ^{7 to} R ¹⁰ are all preferably hydrogen atoms.

  In particular, as the group represented by the formula (3), any group represented by the formulas (4) to (6) is preferable.

In the formula, R ^{7 to} R ³³ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 to carbon atoms. An alkyl group having 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, Or an acyl group having 1 to 20 carbon atoms, and specific examples of these alkoxy groups, thioalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, aryl groups, aralkyl groups, and acyl groups are the same as above. Things.
Among these, R ^{7 to} R ³³ are preferably hydrogen atoms.

  In the present invention, a suitable charge transporting material includes a phenothiazine derivative represented by the formula (7).

In the formula, R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. An alkyl group having 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, Or an acyl group having 1 to 20 carbon atoms, and specific examples of these alkoxy groups, thioalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, aryl groups, aralkyl groups, and acyl groups are the same as above. Things.
Among these, R ^{1 to} R ¹⁰ are all preferably hydrogen atoms.
X ¹ and X ² represent a hydrogen atom, a group represented by the formula (8), a group represented by the formula (9) or a group represented by the formula (10), but represented by the formula (8). Or a group represented by the formula (9) is preferable.

In the formula, R ^{11 to} R ³³ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 to carbon atoms. An alkyl group having 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, Or an acyl group having 1 to 20 carbon atoms, and specific examples of these alkoxy groups, thioalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, aryl groups, aralkyl groups, and acyl groups are the same as above. Things.
Among these, R ^{11 to} R ³³ are preferably hydrogen atoms.

Specific examples of the charge transporting material that can be used in the present invention include those represented by the following formulas (11) to (14), but are not limited thereto.
Among these, the compound represented by the formula (11) or (12) is preferable in consideration of the charge transport property of the obtained thin film and the photoelectric conversion efficiency of the photoelectric conversion element including the thin film.

  In the charge transporting composition of the present invention, the phenothiazine derivative functioning as a charge transporting substance may be used alone or in combination of two or more compounds.

  In addition, as shown in the following scheme, the phenothiazine derivative represented by the above formula (1) includes a phenothiazine compound represented by the formula (15) having a hydrogen atom or the like at positions 3 and 7, and the formula (16) or It can be produced by reacting an arylamine compound represented by the formula (17) in the presence of an oxidizing agent.

（式中、Ｒ¹〜Ｒ⁶、Ａｒ¹およびＡｒ²は、上記と同じ意味を表す。）

(In the formula, R ^{1 to} R ⁶ , Ar ¹ and Ar ² represent the same meaning as described above.)

  The charge ratio of the phenothiazine compound represented by the formula (15) and the arylamine compound represented by the formula (16) or the formula (17) is a substance amount (mol) ratio with respect to the phenothiazine compound 1. About 1 to 10 amine compounds are suitable.

Examples of the oxidizing agent used in the above reaction include halogen-based oxidizing agents such as iodine, and inorganic oxidizing agents such as silver nitrate, potassium nitrate, and potassium permanganate. These oxidizing agents may be used alone or in combination of two or more.
Although the usage-amount of an oxidizing agent can be about 2 mol with respect to 1 mol of aryl compounds represented by Formula (15), about 3 mol is suitable.

  When the starting compounds are all solid or from the viewpoint of efficiently obtaining the target phenothiazine derivative, the above reactions are carried out in a solvent. When a solvent is used, the type is not particularly limited as long as it does not adversely affect the reaction. Specific examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic Group hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), ketones (acetone, methyl ethyl ketone, Methyl isobutyl ketone, di- -Butyl ketone, cyclohexanone, etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), lactams and lactones (N-methylpyrrolidone, γ-butyrolactone, etc.), ureas (N, N-dimethyl) Imidazolidinone, tetramethylurea, etc.), sulfoxides (dimethyl sulfoxide, sulfolane, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.) and the like. These solvents may be used alone or in combination of two or more. You may mix and use.

The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent to be used, but is preferably about 0 to 200 ° C and more preferably 20 to 150 ° C.
After completion of the reaction, the desired phenothiazine derivative can be obtained by post-treatment according to a conventional method.
In particular, in the present invention, it is preferable to use a phenothiazine derivative purified by a method such as reprecipitation or ion exchange. By using the purified one, the characteristics of the OPV element including a thin film obtained from the composition containing the compound can be further improved.

In the organic thin film solar cell, the ionization potential of the hole collection layer is preferably a value close to the ionization potential of the p-type semiconductor material in the active layer. The absolute value of the difference is preferably 0 to 1 eV, more preferably 0 to 0.5 eV, and even more preferably 0 to 0.2 eV.
Therefore, the charge transporting composition of the present invention may contain an electron-accepting dopant material for the purpose of adjusting the ionization potential of the charge transporting thin film obtained using the composition.
The electron-accepting dopant substance is not particularly limited as long as it is soluble in at least one solvent used.

Specific examples of the electron-accepting dopant material include inorganic strong acids such as hydrogen chloride, sulfuric acid, nitric acid and phosphoric acid; aluminum chloride (III) (AlCl ₃ ), titanium tetrachloride (IV) (TiCl ₄ ), boron tribromide (BBr ₃ ), boron trifluoride ether complex (BF ₃ · OEt ₂ ), iron chloride (III) (FeCl ₃ ), copper (II) chloride (CuCl ₂ ), antimony pentachloride (V) (SbCl ₅ ), Lewis acids such as arsenic pentafluoride (V) (AsF ₅ ), phosphorus pentafluoride (PF ₅ ), tris (4-bromophenyl) aluminum hexachloroantimonate (TBPAH); benzenesulfonic acid, tosylic acid, camphorsulfonic acid Hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, dodecylbenzenesulfonic acid, polystyrenesulfonic acid, International Publication No. 2005/000 1,4-benzodioxane disulfonic acid compound described in No. 32, arylsulfonic acid compound described in International Publication No. 2006/025342, dinonylnaphthalene sulfone described in JP-A-2005-108828 Acids, organic strong acids such as 1,3,6-naphthalene trisulfonic acid; 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4- Examples include organic oxidizers such as benzoquinone (DDQ) and iodine, and inorganic oxidizers such as heteropolyacid compounds such as phosphomolybdic acid, phosphotungstic acid, and phosphotungstomolybdic acid described in International Publication No. 2010/058777. These may be used alone or in combination of two or more.

Among the various electron-accepting dopant materials, in the present invention, Bronsted acid that donates H ⁺ is particularly preferable, arylsulfonic acid compounds are more preferable, and arylsulfonic acid compounds represented by formula (D1) are particularly preferable. It is.

（式中、Ｘは、Ｏを表し、Ａは、ナフタレン環またはアントラセン環を表し、Ｂは、２〜４価のパーフルオロビフェニル基を表し、ｌは、Ａに結合するスルホン酸基数を表し、１≦ｌ≦４を満たす整数であり、ｑは、ＢとＸとの結合数を示し、２〜４を満たす整数である。）

(In the formula, X represents O, A represents a naphthalene ring or an anthracene ring, B represents a divalent to tetravalent perfluorobiphenyl group, and l represents the number of sulfonic acid groups bonded to A. (It is an integer satisfying 1 ≦ l ≦ 4, and q represents the number of bonds between B and X, and is an integer satisfying 2 to 4.)

  In the present invention, examples of the arylsulfonic acid compound that can be suitably used include the following compounds (formula (D2)).

Furthermore, you may mix | blend another additive with the charge transportable composition of this invention, as long as the objective of this invention can be achieved.
The kind of additive can be appropriately selected from known ones depending on the desired effect, but the solvent resistance and water resistance of the thin film obtained, the electron blocking property, the HOMO level and the LUMO are improved. It is preferable to add an alkoxysilane or a siloxane-based material from the viewpoint that the level is an optimum value for the active layer.
As the alkoxysilane, any one or more alkoxysilanes among tetraalkoxysilane, trialkoxysilane, dialkoxysilane can be used. In particular, tetraethoxysilane, tetramethoxysilane, phenyltriethoxysilane, phenyltrisilane. Methoxysilane, methyltriethoxysilane, methyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, dimethyldiethoxysilane, and dimethyldimethoxysilane are preferable, and tetraethoxysilane is more preferable.
Examples of the siloxane material include polysiloxanes such as poly (tetraethoxysilane) and poly (phenylethoxysilane) obtained by a reaction such as hydrolysis with respect to the alkoxysilane.
The amount of the alkoxysilane or siloxane-based material added is not particularly limited as long as the above effect is exhibited, but is preferably 0.0001 to 100 times in mass ratio with respect to the phenothiazine derivative used in the present invention. 0.01 to 50 times is more preferable, and 0.05 to 10 times is even more preferable.

  As the solvent used for the preparation of the charge transporting composition, a highly soluble solvent that can dissolve the phenothiazine derivative and the electron-accepting dopant substance satisfactorily can be used. A highly soluble solvent can be used individually by 1 type or in mixture of 2 or more types, The usage-amount can be 5-100 mass% with respect to the whole solvent used for a composition.

Examples of such highly soluble solvents include water; alcohol solvents such as ethanol, 2-propanol, 1-butanol, 2-butanol, s-butanol, t-butanol, 1-methoxy-2-propanol, N Amide systems such as -methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone An organic solvent such as a solvent may be mentioned.
Among these, at least one selected from water and alcohol solvents is preferable, and water, ethanol, and 2-propanol are more preferable.
In particular, when used for the formation of the reverse stacking type OPV hole collection layer, a solvent composed of only one or two or more solvents selected from alcohol solvents and water, which does not adversely affect the active layer. It is preferable to use it.

  Both the charge transporting material and the electron-accepting dopant material are preferably completely dissolved or uniformly dispersed in the above-mentioned solvent. In consideration of obtaining the hole collection layer with good reproducibility, it is more preferable that these substances are completely dissolved in the solvent.

In addition, the charge transporting composition of the present invention has a viscosity of 10 to 200 mPa · s, particularly 35 to 150 mPa · s at 25 ° C. in order to improve the film forming property and the discharge property from the coating apparatus, and is at normal pressure. At least one high-viscosity organic solvent having a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. may be contained.
The high-viscosity organic solvent is not particularly limited. For example, cyclohexanol, ethylene glycol, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butane. Examples thereof include diol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol and the like.

  The addition ratio of the high-viscosity organic solvent to the entire solvent used in the charge transporting composition of the present invention is preferably within a range in which no solid precipitates. As long as no solid precipitates, the addition ratio is 5-80. It is preferable that it is mass%.

Furthermore, other solvents that can provide film flatness during heat treatment for the purpose of improving the wettability to the coated surface, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc., are used in the composition. It is also possible to mix at a ratio of 1 to 90% by mass, preferably 1 to 50% by mass with respect to the whole.
Examples of such a solvent include butyl cellosolve, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl carbitol, Examples include, but are not limited to, diacetone alcohol, γ-butyrolactone, ethyl lactate, and n-hexyl acetate.

The solid content concentration of the charge transporting composition of the present invention is appropriately set in consideration of the viscosity and surface tension of the composition, the thickness of the thin film to be produced, etc. It is about 0.0 mass%, Preferably it is 0.5-5.0 mass%, More preferably, it is 1.0-3.0 mass%.
The mass ratio of the charge transporting substance and the electron-accepting dopant substance is also appropriately set in consideration of the type of charge transporting property, charge transporting substance, etc. that are expressed. On the other hand, the electron-accepting dopant substance is 0 to 10, preferably 0.1 to 3.0, and more preferably 0.2 to 2.0.
The viscosity of the charge transporting composition used in the present invention is appropriately adjusted according to the coating method in consideration of the thickness of the thin film to be produced and the solid content concentration, but is usually 0.1 mPa at 25 ° C. -It is about s-50mPa * s.

  When preparing the charge transporting composition of the present invention, the charge transporting material, the electron accepting dopant material, and the solvent can be mixed in any order as long as the solid content is uniformly dissolved or dispersed in the solvent. That is, for example, after dissolving a phenothiazine derivative in a solvent, a method of dissolving an electron-accepting dopant substance in the solution, a method of dissolving an electron-accepting dopant substance in a solvent, and then dissolving a phenothiazine derivative in the solution, Any method in which a phenothiazine derivative and an electron-accepting dopant substance are mixed and then the mixture is charged into a solvent and dissolved can be employed as long as the solid content is uniformly dissolved or dispersed in the solvent.

  In general, the composition is prepared in an inert gas atmosphere at normal temperature and pressure. However, as long as the compound in the composition is not decomposed or the composition greatly changes, the composition is prepared in an air atmosphere (the presence of oxygen). Below), or while heating.

The hole collection layer of the present invention can be formed by applying the above-described charge transporting composition onto the anode of an organic thin film solar cell and baking it.
In application, considering the viscosity and surface tension of the charge transporting composition, the desired thin film thickness, etc., drop casting method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, What is necessary is just to employ | adopt the optimal thing from various wet process methods, such as the die-coating method, the inkjet method, and the printing method (a relief printing, an intaglio, a planographic printing, screen printing, etc.).
In general, the coating is performed in an inert gas atmosphere at normal temperature and pressure, but in an air atmosphere (in the presence of oxygen) unless the compound in the composition is decomposed or the composition is largely changed. It may be performed while heating.

  The film thickness is not particularly limited, but in any case, it is preferably about 0.1 to 500 nm, more preferably about 1 to 100 nm. Methods for changing the film thickness include methods such as changing the solid content concentration in the composition and changing the amount of solution at the time of coating.

Hereinafter, although the manufacturing method of the order lamination type organic thin film solar cell which used the charge transportable composition of this invention as a composition for hole collection layer formation is demonstrated, it is not limited to these.
[Formation of anode layer]: A step of forming a layer of an anode material on the surface of a transparent substrate to produce a transparent electrode As an anode material, inorganic oxidation such as indium tin oxide (ITO), indium zinc oxide (IZO), etc. Products, metals such as gold, silver, and aluminum, and high charge transporting organic compounds such as polythiophene derivatives and polyaniline derivatives can be used. Of these, ITO is most preferred. As the transparent substrate, a substrate made of glass or transparent resin can be used.
The method of forming the anode material layer (anode layer) is appropriately selected according to the properties of the anode material. Usually, a dry process such as a vacuum deposition method or a sputtering method is selected in the case of a hardly soluble or hardly dispersible sublimation material, and in the case of a solution material or a dispersion material, the viscosity and surface tension of the composition are desired. In consideration of the thickness of the thin film and the like, an optimum one of the above-described various wet process methods is adopted.

Moreover, a commercially available transparent anode substrate can also be used. In this case, from the viewpoint of improving the yield of the element, it is preferable to use a substrate that has been subjected to a smoothing treatment. When using a commercially available transparent anode substrate, the manufacturing method of the organic thin-film solar cell of this invention does not include the process of forming an anode layer.
In the case of forming a transparent anode substrate using an inorganic oxide such as ITO as an anode material, it is preferably used after washing with a detergent, alcohol, pure water or the like before laminating the upper layer. Furthermore, it is preferable to perform surface treatment such as UV ozone treatment and oxygen-plasma treatment immediately before use. When the anode material is mainly composed of an organic material, the surface treatment may not be performed.

[Formation of hole collection layer]: Step of forming a hole collection layer on the formed anode material layer According to the above method, the charge transporting composition of the present invention is used on the anode material layer. A hole collection layer is formed.

[Formation of active layer]: Step of forming an active layer on the formed hole collection layer The active layer is an n layer which is a thin film made of an n-type semiconductor material and a thin film made of a p-type semiconductor material. Even if it laminates | stacks a layer, the non-laminate thin film which consists of a mixture of these materials may be sufficient.

Examples of n-type semiconductor materials include fullerene, [6,6] -phenyl-C ₆₁ -butyric acid methyl ester (PC ₆₁ BM), and [6,6] -phenyl-C ₇₁ -butyric acid methyl ester (PC ₇₁ BM). Can be mentioned. On the other hand, as a p-type semiconductor material, it is described in regioregular poly (3-hexylthiophene) (P3HT), PTB7 represented by the following formula, Japanese Patent Application Laid-Open No. 2009-158921 and International Publication No. 2010/008672. Examples thereof include polymers containing a thiophene skeleton in the main chain such as polymers containing thienothiophene units, phthalocyanines such as CuPC and ZnPC, and porphyrins such as tetrabenzoporphyrin.

Among these, as the n-type material, PC ₆₁ BM and PC ₇₁ BM are preferable, and as the p-type material, polymers including a thiophene skeleton in the main chain such as PTB7 are preferable.
The term “thiophene skeleton in the main chain” as used herein refers to a divalent aromatic ring composed solely of thiophene, or thienothiophene, benzothiophene, dibenzothiophene, benzodithiophene, naphthothiophene, naphthodithiophene, anthrathiophene, anthracodi. It represents a divalent fused aromatic ring containing one or more thiophenes such as thiophene, and these may be substituted with a substituent represented by R ^{1 to} R ⁶ above.

  In the same manner as described above, the active layer is formed by selecting the above-described dry processes when the active layer material is a hardly soluble sublimation material. When the active layer material is a solution material or dispersion material, the viscosity and surface of the composition are selected. In consideration of tension, desired thin film thickness, and the like, an optimum one of the various wet process methods described above is employed.

[Formation of electron collection layer]: Step of forming an electron collection layer on the formed active layer If necessary, between the active layer and the cathode layer for the purpose of improving the efficiency of charge transfer, etc. An electron collection layer may be formed.
Materials for forming the electron collection layer include lithium oxide (Li ₂ O), magnesium oxide (MgO), alumina (Al ₂ O ₃ ), lithium fluoride (LiF), sodium fluoride (NaF), and magnesium fluoride. (MgF ₂ ), strontium fluoride (SrF ₂ ), cesium carbonate (Cs ₂ CO ₃ ), 8-quinolinol lithium salt (Liq), 8-quinolinol sodium salt (Naq), bathocuproine (BCP), 4,7-diphenyl -1,10-phenanthroline (BPhen), polyethyleneimine (PEI), ethoxylated polyethyleneimine (PEIE) and the like.

  In the same manner as described above, when the electron collection material is a hardly soluble sublimation material, the various dry processes described above are selected, and in the case of a solution material or a dispersion liquid material, the method of forming the electron collection layer is selected. In consideration of viscosity, surface tension, desired thin film thickness, and the like, an optimum one of the various wet process methods described above is employed.

[Formation of cathode layer]: Step of forming a cathode layer on the formed electron collection layer As cathode materials, aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium, calcium, Examples include metals such as barium, silver and gold, inorganic oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO), and high charge transporting organic compounds such as polythiophene derivatives and polyaniline derivatives. These cathode materials can be laminated or mixed for use.
The cathode layer is formed in the same manner as described above when the cathode layer material is a poorly soluble, hardly dispersible sublimable material, and the various dry processes described above are selected. In consideration of the viscosity and surface tension of the film, the desired thickness of the thin film, etc., an optimum one of the various wet process methods described above is employed.

[Formation of carrier block layer]
If necessary, a carrier block layer may be provided between arbitrary layers for the purpose of controlling photocurrent rectification. When providing a carrier blocking layer, usually an electron blocking layer is inserted between the active layer and the hole collection layer or anode, and a hole blocking layer is inserted between the active layer and the electron collection layer or cathode. In many cases, this is not the case.
Examples of the material for forming the hole blocking layer include titanium oxide, zinc oxide, tin oxide, bathocuproine (BCP), 4,7-diphenyl 1,10-phenanthroline (BPhen), and the like.
Examples of the material for forming the electron blocking layer include triarylamines such as N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) and poly (triarylamine) (PTAA). Materials and the like.

  In the same manner as described above, the carrier block layer is formed by selecting the various dry processes described above when the carrier block layer material is a poorly soluble, hardly dispersible sublimation material, and when the carrier block layer material is a solution material or a dispersion material, In consideration of the viscosity and surface tension of the composition, the desired thickness of the thin film, etc., an optimum one of the various wet process methods described above is employed.

The OPV device manufactured by the method exemplified above is again introduced into the glove box and sealed in an inert gas atmosphere such as nitrogen in order to prevent device deterioration due to the atmosphere. The function as a solar cell can be exhibited, or the solar cell characteristics can be measured.
As a sealing method, a concave glass substrate with a UV curable resin attached to the end is attached to the film forming surface side of the organic thin film solar cell element in an inert gas atmosphere, and the resin is cured by UV irradiation. Examples of the method include performing a film sealing type sealing by a technique such as sputtering under vacuum.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, the apparatus used is as follows.
(1) NMR
Device: AVANCE III HD manufactured by Bruker
Measurement frequency: 500 MHz
Measurement solvent: Heavy chloroform produced by Kanto Chemical Co., Inc. Internal standard: Tetramethylsilane (δ = 0.00 ppm)
(2) LC-MS
Device: ZQ2000 manufactured by Waters
Column: Intersil ODS-3 (3.0 μm) 2.1 mm D. × 750mm
Eluent: acetonitrile / 0.2% formic acid aqueous solution (70:30)
(3) Glove box: Glove box system manufactured by VAC, USA (4) Vapor deposition equipment: Vacuum vapor deposition equipment, manufactured by Aoyama Engineering Co., Ltd.
(5) Solar simulator: manufactured by Spectrometer Co., Ltd., OTENTOUN-III, AM1.5G filter, radiation intensity: 100 mW / cm ²
(6) Source measure unit: 2612A, manufactured by Keithley Instruments Co., Ltd.
(7) Film thickness measuring device: manufactured by Kosaka Laboratory, Surfcorder ET-4000
(8) Ionization potential measuring device: Riken Keiki Co., Ltd., AC-3

[1] Synthesis of phenothiazine derivative [Synthesis Example 1] Synthesis of phenothiazine derivative A A phenothiazine derivative A was synthesized according to the following scheme (1).

Polymer Chemistry, 2013, Vol. 4, p. Based on the method described in 4182-4191, 4-aminotriphenylamine was obtained according to the following method.
That is, 5.07 g of diphenylamine and 2.23 g of potassium carbonate were dissolved in 40 mL of dimethyl sulfoxide (hereinafter, DMSO), 6.22 g of 4-fluoronitrobenzene was added, and the mixture was reacted at 150 ° C. for 48 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was allowed to cool to room temperature, and the reaction solution was poured into ice water at 0 ° C. to precipitate a solid. The resulting solid was filtered and dried under reduced pressure while heating to 45 ° C. The dried solid was purified by silica gel chromatography (developing solvent: chloroform-hexane (1: 1)) to obtain 3.52 g of 4-nitrotriphenylamine as an orange solid (yield 40%). The result of ¹ H-NMR is shown below.
¹ H-NMR (500 MHz, CDCl ₃ ): δ 6.64 (d, 2H), 6.91 (t, 2H), 6.95 (d, 2H), 7.02 (d, 4H), 7. 19 (t, 4H).

The nitrogen-substitution was performed by dissolving 3.31 g of 4-nitrotriphenylamine obtained above and 0.56 g of 10% palladium carbon in 70 mL of tetrahydrofuran (hereinafter referred to as THF) and 21 mL of ethanol. The Tedlar bag was filled with hydrogen gas and replaced with a hydrogen atmosphere, and then reacted at normal pressure and normal temperature for 24 hours. After completion of the reaction, nitrogen substitution was performed, the reaction solution was filtered through Celite, and the organic solvent of the obtained filtrate was distilled off to obtain a brown solid. The obtained solid was dissolved in chloroform and recrystallized by adding hexane to obtain 2.45 g of brown solid 4-aminotriphenylamine (yield 78%). The result of ¹ H-NMR is shown below.
¹ H-NMR (500 MHz, CDCl ₃ ): δ 6.92 (d, 2H), 7.18-7.22 (m, 6H), 7.37 (t, 4H), 8.40 (d, 2H) ).

0.69 g of phenothiazine and 7.21 g of 4-aminotriphenylamine obtained above were placed in a flask, purged with nitrogen, and dissolved by adding 17.5 mL of dehydrated THF. 2.64 g of iodine was added to the solution and reacted at room temperature for 24 hours. After completion of the reaction, the reaction solution was added to 200 mL of hexane, and the solution was removed by decantation to obtain a purple solid. The obtained solid was dissolved in chloroform, liquid-separated in order of 10% sodium thiosulfate aqueous solution, saturated sodium hydrogen carbonate aqueous solution, and saturated saline, and the washed chloroform solution was dried over sodium sulfate. After filtration, the solvent was distilled off to obtain a purple solid. After purification by silica gel column chromatography (developing solvent: chloroform / ethyl acetate = 1: 1), 1.11 g of a violet phenothiazine derivative A was obtained (yield 45%).
LC / MS (ESI ⁺ ) Retention time 8.4 min m / z; 714 [M + 1] ⁺

[Synthesis Example 2]
A phenothiazine derivative B was synthesized according to the following scheme (2).

11.9 g of phenothiazine and 4.47 g of potassium carbonate were dissolved in 80 mL of DMSO, 12.4 g of 4-fluoronitrobenzene was added, and the mixture was reacted at 150 ° C. for 48 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was allowed to cool to room temperature, and the reaction solution was poured into ice water at 0 ° C. to precipitate a solid. The obtained solid was filtered while washing with a small amount of acetonitrile, and the collected solid was vacuum-dried to obtain a yellow solid. Acetonitrile was added to the obtained solid, the temperature was raised, and the mixture was allowed to cool and recrystallized to obtain 15.3 g of yellow solid 10- (4-nitrophenyl) -phenothiazine (yield 80%). The result of ¹ H-NMR is shown below.
¹ H-NMR (500 MHz, CDCl ₃ ): δ 7.02 (d, 2H), 7.27 (t, 2H), 7.38 (t, 2H), 7.45 (d, 2H), 7. 50 (d, 2H), 8.05 (t, 2H).

7.66 g of 10- (4-nitrophenyl) -phenothiazine obtained above and 1.11 g of 10% palladium carbon were dissolved in 140 mL of THF and 45 mL of ethanol, and nitrogen substitution was performed. The Tedlar bag was filled with hydrogen gas and replaced with a hydrogen atmosphere, and then reacted at normal pressure and normal temperature for 24 hours. After completion of the reaction, nitrogen substitution was performed, the reaction solution was filtered through Celite, and the organic solvent in the obtained filtrate was distilled off to obtain a purple solid. The obtained solid was dissolved in chloroform and recrystallized by adding hexane to obtain 6.14 g of white solid 4- (10H-phenothiazinyl) aniline (yield 89%). The result of ¹ H-NMR is shown below.
¹ H-NMR (500 MHz, CDCl ₃ ): δ 3.84 (s, 2H), 6.24 (d, 2H), 6.76 (d, 2H), 6.82 (t, 2H), 6. 87 (d, 2H), 6.96 (d, 2H), 7.15 (d, 2H).

0.52 g of phenothiazine and 1.97 g of iodine were placed in a flask, purged with nitrogen, and dissolved by adding 5 mL of dehydrated THF. 6.01 g of 4- (10H-phenothiazinyl) aniline obtained above is put in another flask, dissolved in 20 mL of dehydrated THF, and the obtained solution is dropped into a mixed solution of phenothiazine and iodine, and reacted at room temperature for 24 hours. I let you. After completion of the reaction, the reaction solution was added to 300 mL of hexane, and the solution was removed by decantation to obtain a purple solid. The obtained solid was dissolved in chloroform, liquid-separated in order of 10% sodium thiosulfate aqueous solution, saturated sodium hydrogen carbonate aqueous solution, and saturated saline, and the washed chloroform solution was dried over sodium sulfate. After filtration, the solvent was distilled off to obtain a purple solid. After purification by silica gel column chromatography (developing solvent: chloroform / ethyl acetate = 2: 1), 0.32 g of a phenothiazine derivative B as a purple solid was obtained (yield 16%).
LC / MS (ESI ⁺ ) Retention time 7.6 minutes m / z; 774 [M + 1] ⁺

[2] Preparation of active layer composition [Preparation Example 1]
2.0 mL of chlorobenzene was added to a sample bottle containing 20 mg of PTB7 (manufactured by 1-Material) and 30 mg of PC ₆₁ BM (manufactured by Frontier Carbon Co., Ltd., product name: nanom spectra E100). Stir for hours. After allowing this solution to cool to room temperature, 60 μL of 1,8-diiodooctane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred to obtain a solution A1 (active layer composition).

[3] Production of composition for hole collection layer [Example 1-1]
To the phenothiazine derivative A 54.7 mg obtained in Synthesis Example 1, 69.2 mg of the aryl sulfonic acid compound A represented by the above formula (D2) synthesized based on the description of WO 2006/025342 is added. A blue solution was obtained by dissolving it in a mixed solvent of 00 g and 2.00 g of cyclohexanol. The obtained blue solution was filtered with a syringe filter having a pore diameter of 0.20 μm to obtain a hole collection layer composition B1.

[Example 1-2]
Except having changed the phenothiazine derivative A into the phenothiazine derivative B, it carried out similarly to Example 1-1, and obtained composition B2 for positive hole collection layers.

[4] Production of organic thin film solar cell [Example 2-1]
For the hole collection layer prepared in Example 1-1 on the substrate after UV / ozone treatment of a 20 mm × 20 mm glass substrate obtained by patterning the ITO transparent conductive layer serving as the anode into a 2 mm × 20 mm stripe pattern, for 15 minutes. Composition B1 was applied by spin coating. This glass substrate was heated at 230 ° C. for 10 minutes using a hot plate to form a hole collection layer. The film thickness of the hole collection layer was about 30 nm.
Thereafter, in a glove box substituted with an inert gas, the solution A1 obtained in Preparation Example 1 is dropped onto the hole collection layer formed, and a film is formed by a spin coating method to form an active layer having a thickness of 100 nm. Formed.
Next, the substrate on which the organic semiconductor layer is formed and the negative electrode mask are placed in a vacuum vapor deposition apparatus, and the vacuum in the apparatus is evacuated to 1 × 10 ⁻³ Pa or less. A lithium 8-hydroxyquinolinolato layer serving as a collection layer was deposited to a thickness of 1 nm.
Finally, an aluminum layer serving as a negative electrode was deposited to a thickness of 80 nm by a resistance heating method, thereby manufacturing an OPV element having an area where the stripe-shaped ITO layer intersects with the aluminum layer was 2 mm × 2 mm. .

[Example 2-2]
An OPV element was produced in the same manner as in Example 2-1, except that the hole collection layer composition B2 was used instead of the hole collection layer composition B1.

[Example 2-3]
An OPV element was produced in the same manner as in Example 2-1, except that the hole collection layer composition B3 was used instead of the hole collection layer composition B1.

[Comparative Example 2-1]
An OPV element was produced in the same manner as in Example 2-1, except that the hole collection layer was not formed.

[5] Characteristic evaluation About each OPV element produced by the said Examples 2-1 to 2-2 and the comparative example 2-1, a short circuit current density (Jsc [mA / cm < ² >]), an open circuit voltage (Voc [V]) , Curve factor (FF), and PCE [%] were evaluated. The results are shown in Table 1.
PCE [%] was calculated by the following equation.
PCE [%] = Jsc [mA / cm ² ] × Voc [V] × FF ÷ incident light intensity (100 [mW / cm ² ]) × 100

As shown in Table 1, an OPV device comprising a thin film obtained from the composition for a hole collection layer of the present invention as a hole collection layer is compared with an OPV device having no hole collection layer. Relatively high PCE.
Thus, it turns out that the photoelectric conversion characteristic of an OPV element can be improved by using the composition for positive hole collection layers of this invention.

Claims (21)

A charge transporting composition comprising a charge transporting substance comprising a phenothiazine derivative represented by formula (1) or formula (2) and a solvent.

(In Formula (1) and (2), R < ¹ > -R < ⁶ > is mutually independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C1-C20 alkoxy group, a C1-C20 Thioalkoxy group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon Represents an aralkyl group having 7 to 20 carbon atoms or an acyl group having 1 to 20 carbon atoms,
Ar ¹ and Ar ² are each independently substituted, optionally substituted phenyl group, biphenyl group, anthryl group, phenanthryl group, fluorenyl group, terphenyl group, tetracenyl group, pentacenyl group, perylenyl group, thienyl group, Aromatics selected from furyl, oxazolyl, thiazolyl, imidazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, pyrazyl, quinolyl, quinoxalyl, benzoxazolyl, benzothiazolyl, and benzoimidazolyl Represents a group. ) The charge transporting composition according to claim 1, wherein Ar ¹ and Ar ^{2 in the} formulas (1) and (2) are independently of each other a group represented by the formula (3).

(In the formula, Ar ³ and Ar ⁴ are each independently a hydrogen atom or an aromatic group optionally substituted with an amino group, a phenylamino group, a diphenylamino group, an alkoxy group, an alkylthio group or an alkyl group. This aromatic group is a phenyl group, biphenyl group, anthryl group, phenanthryl group, fluorenyl group, terphenyl group, tetracenyl group, pentacenyl group, perylenyl group, thienyl group, furyl group, oxazolyl group, thiazolyl group, imidazolyl group , Pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, pyrazyl group, quinolyl group, quinoxalyl group, benzoxazolyl group, benzothiazolyl group, and benzoimidazolyl group, provided that Ar ³ and Ar ⁴ are simultaneously selected. Never become a hydrogen atom, For r ³ and Ar ⁴ are both aromatic groups, even if they are bound by a single bond to each other may be bonded through a hetero atom.
R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. Group, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, or carbon number 1 to 20 acyl groups are represented. ) The charge transporting composition according to claim 1, wherein the group represented by the formula (3) is any group represented by the formulas (4) to (6).

(In the formula, R ^{7 to} R ³³ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms.) The charge transporting composition according to claim 1, wherein the charge transporting substance is a phenothiazine derivative represented by the formula (7).

{In the formula, R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms,
X ¹ and X ² represent a hydrogen atom, a group represented by the formula (8), a group represented by the formula (9) or a group represented by the formula (10).

(In the formula, R ^{11 to} R ³³ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms.)} The charge transporting composition according to claim 4, wherein X ¹ and X ² are a group represented by the formula (8) or a group represented by the formula (9). 6. The charge transporting composition according to claim 4, wherein R ^{1 to} R ³³ are hydrogen atoms.   Furthermore, the charge transportable composition of any one of Claims 1-6 containing an electron-accepting dopant substance. The charge transporting composition according to claim 7, wherein the electron-accepting dopant material is an aryl sulfonic acid compound represented by the formula (D1).

(In the formula, X represents O, A represents a naphthalene ring or an anthracene ring, B represents a divalent to tetravalent perfluorobiphenyl group, and l represents the number of sulfonic acid groups bonded to A. (It is an integer satisfying 1 ≦ l ≦ 4, and q represents the number of bonds between B and X, and is an integer satisfying 2 to 4.)   It is an object for hole collection layers of an organic photoelectric conversion element, The charge transportable composition of any one of Claims 1-8.   The charge transporting composition according to claim 9, wherein the organic photoelectric conversion element is an organic thin film solar cell or an optical sensor.   The hole collection layer of the organic photoelectric conversion element formed using the charge transportable composition of Claim 9 or 10.   The organic photoelectric conversion element which has the positive hole collection layer of Claim 11, and the active layer provided so that it might be in contact with it.   The organic photoelectric conversion element according to claim 12, wherein the active layer contains a fullerene derivative.   The organic photoelectric conversion element according to claim 12, wherein the active layer contains a polymer containing a thiophene skeleton in the main chain.   The organic photoelectric conversion element according to claim 12, wherein the active layer contains a fullerene derivative and a polymer containing a thiophene skeleton in the main chain.   It is an organic thin film solar cell or an optical sensor, The organic photoelectric conversion element of any one of Claims 12-15. A phenothiazine derivative represented by the formula (1) or (2):

(In Formula (1) and (2), R < ¹ > -R < ⁶ > is mutually independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C1-C20 alkoxy group, a C1-C20 Thioalkoxy group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon Represents an aralkyl group having 7 to 20 carbon atoms or an acyl group having 1 to 20 carbon atoms,
Ar ¹ and Ar ² are each independently a substituted phenyl group, an optionally substituted biphenyl group, anthryl group, phenanthryl group, fluorenyl group, terphenyl group, tetracenyl group, pentacenyl group, perylenyl group, thienyl group , A furyl group, an oxazolyl group, a thiazolyl group, an imidazolyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a pyrazyl group, a quinolyl group, a quinoxalyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group Represents a group. ) The phenothiazine derivative according to claim 17, wherein Ar ¹ and Ar ^{2 in the} formulas (1) and (2) are independently of each other a group represented by the formula (3).

(In the formula, Ar ³ and Ar ⁴ may be independently of each other a hydrogen atom or an amino group, a phenylamino group, a diphenylamino group, a triphenylamino group, an alkoxy group, an alkylthio group or an alkyl group. Represents a good aromatic group, and this aromatic group includes a phenyl group, a biphenyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a terphenyl group, a tetracenyl group, a pentacenyl group, a perylenyl group, a thienyl group, a furyl group, an oxazolyl group, thiazolyl group, an imidazolyl group, a pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, pyrazinyl group, quinolyl group, a quinoxalyl group, benzoxazolyl group, benzothiazolyl group a group selected from and benzimidazolyl group. However, Ar ³ and Ar ⁴ is a hydrogen atom at the same time Not Rukoto, also when both the aromatic groups Ar ³ and Ar ⁴ is, even if they are bound by a single bond to each other may be bonded through a hetero atom.
R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. Group, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, or carbon number 1 to 20 acyl groups are represented. ) The phenothiazine derivative according to claim 18, wherein the group represented by the formula (3) is any group represented by the formulas (4) to (6).

(In the formula, R ^{7 to} R ³³ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms.) The phenothiazine derivative according to claim 17, which is represented by formula (7).

{In the formula, R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms,
X ¹ and X ² represent a group represented by the formula (8), a group represented by the formula (9), or a group represented by the formula (10).

(In the formula, R ^{11 to} R ³³ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkyl group, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, haloalkyl group having 1-20 carbon atoms, aryl group having 6-20 carbon atoms, aralkyl group having 7-20 carbon atoms. Or an acyl group having 1 to 20 carbon atoms.)} The phenothiazine derivative according to claim 17, which is represented by formula (11) or (12).