TW202128821A - Copolymer and organic photovoltaic element - Google Patents

Abstract

Disclosed is a copolymer as an electron donor material and an organic photovoltaic element containing the same. The copolymer has a wide absorption wavelength distribution and a high absorption in the ultraviolet-visible light region. Thus, the copolymer can be used as an electron donor material with a wide energy gap, so that the copolymer has excellent photoelectric conversion characteristics.

Description

Copolymer and organic photovoltaic element

The present invention relates to a copolymer that can be used as an electron donor material and an organic photovoltaic element containing the copolymer, in particular to a copolymer containing a quinoxaline derivative group in the main chain and containing the copolymer Organic photovoltaic elements.

As the times evolve, the consumption of energy resources such as coal, oil, natural gas, and nuclear energy is increasing, and the energy crisis is relatively emerging, so solar power generation has been developed. Solar power generation is a renewable and environmentally friendly power generation method that can reduce environmental pollution. The first-generation solar cells are mainly silicon based solar cells, which have a high photoelectric conversion rate. The second-generation solar cell is a thin-film cadmium telluride (CdTe) solar cell, but the toxicity of its raw materials and the manufacturing process cause greater environmental pollution. As a result, third-generation organic solar cells have emerged, including dye-sensitized solar cells (DSSC), nanocrystalline cells, or organic photovoltaics (OPV). Compared with inorganic materials that need to be coated by a vacuum process, organic photovoltaic elements can be made by dip coating, spin coating, slit coating, screen printing, inkjet printing, etc., so it is easier to achieve low-cost and large-scale production Economic benefits. Among them, the new generation of organic photovoltaic devices are manufactured using electron acceptor materials and electron donor materials (copolymers) as the materials of the active layer (light absorbing layer). The new generation of organic photovoltaic elements has several advantages: (1) light weight and low production cost; (2) flexibility; (3) device structure can be designed; (4) suitable for liquid-phase manufacturing process, Large area wet coating.

Although organic photovoltaic elements have many advantages, most of the current developments in electron acceptor materials are based on fullerene derivatives (such as PC ₆₀ BM and PC ₇₀ BM), but fullerene derivatives themselves have the following shortcomings : Easy to dimerize under light, easy to crystallize when heated, weak absorption in the visible light region, difficult to modify and purify the structure, expensive, etc. Therefore, in recent years, various circles have actively developed non-fullerene electron acceptor materials in order to achieve higher performance. However, because non-fullerene electron acceptor materials are narrow band gap materials, the electron donor materials matched with them need to have Wide energy gap characteristics.

Therefore, the development of electron donor materials (copolymers) with wide energy gaps, which can be used as the active layer of organic photovoltaic devices in combination with non-fullerene electron acceptor materials, thereby effectively improving the energy conversion of organic photovoltaic devices Efficiency (PCE) has become the goal of current research.

In view of the problems of existing organic photovoltaic elements, the present invention provides a copolymer that can be used as an electron donor material, which can be used with non-fullerene electron acceptor materials to serve as an active layer of an organic photovoltaic element. Since the copolymer of the present invention has a wide absorption wavelength distribution and high absorption in the ultraviolet-visible light region, the copolymer can be used as an electron donor material with a wide energy gap, so the absorption in the visible light region can be improved to improve the The matching of the energy levels of the non-fullerene electron acceptor materials enables the organic photovoltaic device to have excellent photoelectric conversion characteristics and good energy conversion efficiency (PCE).

Therefore, the first object of the present invention is to provide a copolymer of the first aspect.

其中， W為

， Y為

， Z為

， W、Y與Z彼此不相同； a、b與c皆為實數，且0≦a≦1，0≦b≦1，0≦c≦1，並a、b與c的和為1； p、p′、q、q′、r與r′分別為0、1或2； A¹ 、A² 與A³ 分別為下列式(1)或式(2)所示的基團，且至少一個存在於化學式(I)中的A¹ 、A² 或A³ 為式(1)所示的基團； [式(1)]

[式(2)]

R¹ 與R² 分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 、芳基或雜芳基； G與L分別為H、F或Cl，且G與L其中一者為Cl； R⁵ 至R⁸ 分別為未經取代或經至少一R¹⁸ 取代的C₄ ~C₃₀ 直鏈、支鏈或環狀烷基、未經取代或經至少一R¹⁸ 取代的C₄ ~C₃₀ 烯基、或未經取代或經至少一R¹⁸ 取代的C₄ ~C₃₀ 炔基； R¹⁸ 為鹵素、‒CN或‒SiR¹⁹ R²⁰ R²¹ ； R¹⁹ 至R²¹ 分別為C₁ ~C₃₀ 烷基； R⁰ 為‒NH‒、‒NR²² ‒、亞芳基(arylene；即二價的芳基)或亞雜芳基(heteroarylene；即二價的雜芳基)； R²² 為C₁ ~C₃₀ 烷基、芳基或雜芳基；及 Ar¹ 至Ar⁹ 分別為亞芳基或亞雜芳基。Therefore, the copolymer of the first aspect of the present invention includes the structure represented by the following chemical formula (I): [Chemical formula (I)]

Where W is

, Y is

, Z is

, W, Y, and Z are different from each other; a, b, and c are all real numbers, and 0≦a≦1, 0≦b≦1, 0≦c≦1, and the sum of a, b, and c is 1; p , P', q, q', r and r'are 0, 1 or 2 respectively; A ¹ , A ² and A ³ are groups represented by the following formula (1) or formula (2), and at least one ^{A 1} , A ² or A ³ in the chemical formula (I) is a group represented by the formula (1); [formula (1)]

[Equation (2)]

R ¹ and R ² are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl or heteroaryl, respectively; G and L are H, F or Cl, and one of G and L is Cl; R ⁵ to R ⁸ are respectively unsubstituted or substituted with at least one R ¹⁸ C ₄ to C ₃₀ linear, branched or cyclic alkyl, unsubstituted unsubstituted or substituted with at least one R ¹⁸ is C ₄ ~ C ₃₀ alkenyl group, or unsubstituted or substituted at least by one R ¹⁸ is C ₄ ~ C ₃₀ alkynyl group; R ¹⁸ is halogen, -CN, or -SiR ¹⁹ R ²⁰ R ²¹ ; R ¹⁹ to R ²¹ are C ₁ ~C ₃₀ alkyl groups respectively; R ⁰ is ‒NH‒, ‒NR ²² ‒, arylene (divalent aryl) or heteroarylene (heteroarylene) ; That is, a divalent heteroaryl group); R ²² is a C ₁ to C ₃₀ alkyl group, an aryl group, or a heteroaryl group; and Ar ¹ to Ar ⁹ are respectively an arylene group or a heteroarylene group.

Therefore, the second object of the present invention is to provide a copolymer of the second aspect.

其中， p與p′分別為0、1或2； A¹ 為下列式(1)所示的基團 [式(1)]

R¹ 與R² 相同，且分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 、芳基或雜芳基； G與L分別為H、F或Cl，且G與L其中一者為Cl； Ar² 與Ar³ 分別為亞芳基或亞雜芳基； Ar¹ 為

； R³ 與R⁴ 分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、 ‒C(=O)OR⁸ 、芳基、‒Si(R⁹ )₃ 或

； n₂ 為1、2、3、4或5； R¹¹ 至R¹³ 分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 或‒Si(R⁹ )₃ ； R⁵ 至R⁹ 分別為未經取代或經至少一R¹⁸ 取代的C₄ ~C₃₀ 直鏈、支鏈或環狀烷基、未經取代或經至少一R¹⁸ 取代的C₄ ~C₃₀ 烯基、或未經取代或經至少一R¹⁸ 取代的C₄ ~C₃₀ 炔基； R¹⁸ 為鹵素、‒CN或‒SiR¹⁹ R²⁰ R²¹ ；及 R¹⁹ 至R²¹ 分別為C₁ ~C₃₀ 烷基。Therefore, the copolymer of the second aspect of the present invention includes the structure represented by the following chemical formula (II): [Chemical formula (II)]

Wherein, p and p'are 0, 1 or 2 respectively; A ¹ is a group represented by the following formula (1) [formula (1)]

R ¹ is the ^{same as R 2} and are respectively H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl or heteroaryl; G and L respectively Is H, F or Cl, and one of G and L is Cl; Ar ² and Ar ³ are respectively arylene or heteroarylene; Ar ¹ is

; R ³ and R ⁴ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl, ‒Si(R ⁹ ) ₃ or

; N ₂ is 1, 2, 3, 4 or 5; R ¹¹ to R ¹³ are respectively H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ or ‒Si(R ⁹ ) ₃ ; R ⁵ to R ⁹ are C ₄ to C ₃₀ linear, branched or cyclic alkyl that is unsubstituted or substituted with at least one R ^{18, unsubstituted or substituted with at least one R 18} substituted C ₄ ~C ₃₀ alkenyl, or unsubstituted or substituted with at least one R ¹⁸ C ₄ ~C ₃₀ alkynyl; R ¹⁸ is halogen, ‒CN or ‒SiR ¹⁹ R ²⁰ R ²¹ ; and R ¹⁹ To R ²¹ are C ₁ to C ₃₀ alkyl groups, respectively.

Therefore, the third object of the present invention is to provide a third aspect of the copolymer.

其中， W為

， Y為

， W與Y彼此不相同； a與b皆為實數，且0>a>1，0>b>1，並a與b的和為1； p、p′、q與q′分別為0、1或2； A¹ 與A² 分別為下列式(1)或式(2)所示的基團，且A¹ 與A² 至少一者為式(1)所示的基團； [式(1)]

[式(2)]

R¹ 與R² 分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 、芳基或雜芳基； G與L分別為H、F或Cl，且G與L其中一者為Cl； R⁵ 至R⁸ 分別為未經取代或經至少一R¹⁸ 取代的C₄ ~C₃₀ 直鏈、支鏈或環狀烷基、未經取代或經至少一R¹⁸ 取代的C₄ ~C₃₀ 烯基、或未經取代或經至少一R¹⁸ 取代的C₄ ~C₃₀ 炔基； R¹⁸ 為鹵素、‒CN或‒SiR¹⁹ R²⁰ R²¹ ； R¹⁹ 至R²¹ 分別為C₁ ~C₃₀ 烷基； R⁰ 為‒NH‒、‒NR²² ‒、亞芳基或亞雜芳基； R²² 為C₁ ~C₃₀ 烷基、芳基或雜芳基；及 Ar¹ 至Ar⁶ 分別為亞芳基或亞雜芳基。Therefore, the third aspect of the copolymer of the present invention includes the structure shown in the following chemical formula (III): [Chemical formula (III)]

Where W is

, Y is

, W and Y are different from each other; a and b are real numbers, and 0>a>1, 0>b>1, and the sum of a and b is 1; p, p′, q, and q′ are 0, 1 or 2; A ¹ and A ² are groups represented by the following formula (1) or formula (2) respectively, and ^{at least one of A 1} and A ^{2 is} a group represented by formula (1); [formula( 1)]

[Equation (2)]

R ¹ and R ² are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl or heteroaryl, respectively; G and L are H, F or Cl, and one of G and L is Cl; R ⁵ to R ⁸ are respectively unsubstituted or substituted with at least one R ¹⁸ C ₄ to C ₃₀ linear, branched or cyclic alkyl, unsubstituted unsubstituted or substituted with at least one R ¹⁸ is C ₄ ~ C ₃₀ alkenyl group, or unsubstituted or substituted at least by one R ¹⁸ is C ₄ ~ C ₃₀ alkynyl group; R ¹⁸ is halogen, -CN, or -SiR ¹⁹ R ²⁰ R ²¹ ; R ¹⁹ to R ²¹ are C ₁ ~C ₃₀ alkyl groups; R ⁰ is ‒NH‒, ‒NR ²² ‒, arylene or heteroarylene; R ²² is C ₁ ~C ₃₀ alkyl, Aryl or heteroaryl; and Ar ¹ to Ar ⁶ are arylene or heteroarylene, respectively.

Therefore, the fourth object of the present invention is to provide an organic photovoltaic element.

Therefore, the organic photovoltaic element of the present invention includes any of the aforementioned copolymers.

The effect of the present invention is: because the copolymer of the present invention can be used as an electron donor material contains a weak electron withdrawing group [formula (1) or formula (2)] and an electron donating group [Ar ¹ , Ar ⁴ or Ar ⁷ ], so when the copolymer of the present invention is used as an electron donor material, the absorption spectrum and the energy level of the material can be controlled in a wide range by the combination of the weak electron withdrawing group and the electron donating group on the main chain. In the range of the energy gap. In addition, when the copolymer used as an electron donor material of the present invention is matched with a non-fullerene electron acceptor material, it can have excellent photoelectric conversion characteristics. In other words, when the copolymer of the present invention is used as the electron donor material, the energy conversion efficiency of the organic photovoltaic element can be effectively improved.

The content of the present invention will be described in detail below:

[ Copolymer of the first aspect ]

。The first embodiment of the copolymer of the present invention includes the structure represented by the following chemical formula (I): [Chemical formula (I)]

.

。W is

.

。Y is

.

。Z is

.

W, Y, and Z are different from each other.

a, b, and c are all real numbers representing the Mohr fraction, and 0≦a≦1, 0≦b≦1, 0≦c≦1, and the sum of a, b, and c is 1. Preferably, 0>a≤1, 0≤b>1, 0≤c>1, and the sum of a, b, and c is 1. Preferably, a is 1 and b and c are 0. Preferably, a and b are not 0 and c is 0, and the sum of a and b is 1. More preferably, a=b=0.5, and c is 0. Preferably, a, b, and c are not 0 and the sum of a, b, and c is 1. More preferably, 0.005≤a≤0.99, 0.005≤b≤0.99, 0.005≤c≤0.99, and the sum of a, b, and c is 1.

p, p', q, q', r and r'are 0, 1, or 2, respectively. Preferably, p, p', q, q', r and r'are 0 or 1, respectively. More preferably, p, p', q, q', r and r'are all 1.

[式(2)]

A ¹ , A ² and A ³ are groups represented by the following formula (1) or formula (2) respectively, and at least one of A ¹ , A ² or A ³ present in the chemical formula (I) is the formula (1) The group shown. A ¹ , A ² and A ³ may be the same or different from each other, for example ^{, at least two of A 1} , A ² and A ³ are the same group or different groups, or A ¹ , A ² and A ^{All 3} are the same group or all are different groups. [Formula 1)]

[Equation (2)]

For "at least one of A ¹ , A ² or A ³ in the chemical formula (I) is a group represented by the formula (1)", for example, only A ^{1 is} present in the chemical formula (I) (that is, a is not 0, b and c are all 0), A ^{1 is} the group represented by formula (1); for example, only A ¹ and A ² exist in formula (I) (that is, neither a nor b is 0, c is 0), ^{at least one of A 1} and A ^{2 is} a group represented by formula (1); for example, A ¹ , A ² and A ³ all exist in chemical formula (I) (ie a , B and c are not 0), ^{at least one of A 1} , A ² and A ^{3 is} a group represented by formula (1).

R ¹ and R ² are respectively H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl or heteroaryl. Preferably, when a=1 and b and c are 0, R ¹ and R ² are the same group. Preferably, when a=1 and b and c are 0, R ¹ and R ² are different groups.

G and L are H, F, or Cl, respectively, and one of G and L is Cl. Preferably, one of G and L is Cl, and the other is H.

R ⁵ to R ⁸ are each unsubstituted or substituted with at least one R ¹⁸ is C ₄ ~ C ₃₀ straight-chain, branched or cyclic alkyl, unsubstituted or substituted with at least one R ¹⁸ is C ₄ ~ C ₃₀ Alkenyl, or unsubstituted or C ₄ ~C ₃₀ alkynyl substituted with at least one R ¹⁸ ; R ¹⁸ is halogen, ‒CN or ‒SiR ¹⁹ R ²⁰ R ²¹ . R ¹⁹ to R ²¹ are each a C ₁ to C ₃₀ alkyl group.

R ⁰ is ‒NH‒, ‒NR ²² ‒, arylene or heteroarylene; R ²² is C ₁ ~C ₃₀ alkyl, aryl or heteroaryl. Preferably, R ⁰ is ‒NR ²² ‒, a substituted or unsubstituted divalent phenyl group, a substituted or unsubstituted divalent thienyl group, or a substituted or unsubstituted divalent pyrazinyl group. More preferably, R ⁰ is a divalent thienyl group substituted with a C ₄ to C _{30 branched chain alkyl group.} Still more preferably, R ⁰ is a divalent thienyl group substituted with a C ₄ to C _{12 branched chain alkyl group.}

Ar ¹ to Ar ⁹ may be the same as each other or different, for example, Ar ¹ to Ar ⁹ has at least two of the same group or different groups, or Ar ¹ to Ar ⁹ are all the same groups or both Are different groups.

， 且R³ 與R⁴ 分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 、芳基、雜芳基或‒Si(R⁹ )₃ ，且R⁹ 與R⁵ 的定義相同。Ar¹ 、Ar⁴ 及Ar⁷ 彼此為相同或不相同的基團，例如Ar¹ 、Ar⁴ 及Ar⁷ 中至少有兩者為相同的基團或不相同的基團，或Ar¹ 、Ar⁴ 及Ar⁷ 皆為相同的基團或皆為不相同的基團。Preferably, Ar ¹ , Ar ⁴ and Ar ⁷ are respectively

, And R ³ and R ⁴ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl, heteroaryl, or ‒Si(R ⁹ ) ₃ , and R ⁹ has the same definition as ^{R 5.} Ar ¹ , Ar ⁴ and Ar ⁷ are the same or different groups, for example ^{, at least two of Ar 1} , Ar ⁴ and Ar ⁷ are the same group or different groups, or Ar ¹ , Ar ⁴ And Ar ⁷ are all the same group or all are different groups.

，且n₁ 為1、2、3、4或5；及R¹⁰ 為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 或‒Si(R⁹ )₃ 。Preferably, the aryl group in ^{R 1} to R ^{4 is}

, And n ₁ is 1, 2, 3, 4 or 5; and R ¹⁰ is H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ or ‒Si (R ⁹ ) ₃ .

，且n₂ 為1、2、3、4或5；及R¹¹ 至R¹³ 分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 或‒Si(R⁹ )₃ 。Preferably, the heteroaryl group in ^{R 1} to R ^{4 is}

, And n ₂ is 1, 2, 3, 4, or 5; and R ¹¹ to R ¹³ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR, respectively ⁸ or ‒Si(R ⁹ ) ₃ .

，且n₂ 為1；及R¹¹ 至R¹³ 分別為H、F、Cl或C₄ ~C₃₀ 支鏈烷基。又更佳地，R¹¹ 至R¹³ 分別為H、F、Cl或C₄ ~C₁₂ 支鏈烷基。More preferably, R ¹ to R ⁴ are respectively

, And n ₂ is 1; and R ¹¹ to R ¹³ are respectively H, F, Cl or C ₄ ~C ₃₀ branched chain alkyl. Still more preferably, R ¹¹ to R ¹³ are respectively H, F, Cl or C ₄ to C ₁₂ branched alkyl.

、

或

。More preferably, Ar ¹ , Ar ⁴ and Ar ⁷ are respectively

,

or

.

或

，且n₃ 與n₄ 分別為1、2或3；及R¹⁴ 至R¹⁷ 分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 、芳基或雜芳基。Ar² 、Ar³ 、Ar⁵ 、Ar⁶ 、Ar⁸ 及Ar⁹ 彼此為相同或不相同的基團，例如Ar² 、Ar³ 、Ar⁵ 、Ar⁶ 、Ar⁸ 及Ar⁹ 中至少兩者為相同的基團或不相同的基團，或Ar² 、Ar³ 、Ar⁵ 、Ar⁶ 、Ar⁸ 及Ar⁹ 皆為相同的基團或皆為不相同的基團。Preferably, Ar ² , Ar ³ , Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ are respectively

or

, And n ₃ and n ₄ are 1, 2 or 3 respectively; and R ¹⁴ to R ¹⁷ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR, respectively ^8. Aryl or heteroaryl. Ar ² , Ar ³ , Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ are the same or different from each other, for example, at least two of ^{Ar 2} , Ar ³ , Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ^{9 are} The same group or different groups, or Ar ² , Ar ³ , Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ are all the same group or all are different groups.

。More preferably, Ar ² , Ar ³ , Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ are respectively

.

[ The second aspect of copolymer ]

。The second embodiment of the copolymer of the present invention includes the structure represented by the following chemical formula (II): [Chemical formula (II)]

.

p and p'are 0, 1, or 2, respectively. Preferably, p and p'are 1 respectively.

。A ¹ is a group represented by the following formula (1): [Formula (1)]

.

R ¹ is the ^{same as R 2} and are respectively H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl or heteroaryl.

G and L are H, F, or Cl, respectively, and one of G and L is Cl. Preferably, one of G and L is Cl, and the other is H.

，其中，R³ 與R⁴ 分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 、芳基、‒Si(R⁹ )₃ 或

；n₂ 為1、2、3、4或5；R¹¹ 至R¹³ 分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 或‒Si(R⁹ )₃ 。較佳地，R¹¹ 至R¹³ 中至少一者為F或Cl。Ar ¹ is

, Where R ³ and R ⁴ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl, ‒Si(R ⁹ ) ₃ or

; N ₂ is 1, 2, 3, 4 or 5; R ¹¹ to R ¹³ are respectively H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ or ‒Si(R ⁹ ) ₃ . Preferably, ^{at least one of R 11} to R ¹³ is F or Cl.

Each of R ⁵ to R ⁹ is unsubstituted or substituted with at least one R ¹⁸ is C ₄ ~ C ₃₀ straight-chain, branched or cyclic alkyl, unsubstituted or substituted with at least one R ¹⁸ is C ₄ ~ C ₃₀ Alkenyl, or unsubstituted or C ₄ ~C ₃₀ alkynyl substituted with at least one R ¹⁸ ; R ¹⁸ is halogen, ‒CN or ‒SiR ¹⁹ R ²⁰ R ²¹ ; and R ¹⁹ to R ²¹ are each C ₁ ~ C ₃₀ alkyl.

、

或

。Preferably, Ar ¹ is

,

or

.

或

，且n₃ 與n₄ 分別為1、2或3；及R¹⁴ 至R¹⁷ 分別為H、F、Cl、R⁵ 、‒CN、‒OR⁶ 、‒SR⁷ 、‒C(=O)OR⁸ 、芳基或雜芳基。Ar ² and Ar ³ are respectively an arylene group or a heteroarylene group. Preferably, Ar ² and Ar ³ are respectively

or

, And n ₃ and n ₄ are 1, 2 or 3 respectively; and R ¹⁴ to R ¹⁷ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR, respectively ^8. Aryl or heteroaryl.

[ Third aspect of copolymer ]

。The third embodiment of the copolymer of the present invention includes the structure shown in the following chemical formula (III): [Chemical formula (III)]

.

。W is

.

。Y is

.

W and Y are different from each other.

Both a and b are real numbers representing the Mohr fraction, and 0>a>1, 0>b>1, and the sum of a and b is 1. Preferably, 0.2≦a≦0.8, 0.2≦b≦0.8, and the sum of a and b is 1.

p, p', q and q'are 0, 1, or 2, respectively. Preferably, p, p', q and q'are 1 respectively.

[式(2)]

A ¹ and A ² are groups represented by the following formula (1) or formula (2) respectively, and ^{at least one of A 1} and A ^{2 is} a group represented by formula (1); [Formula (1)]

[Equation (2)]

R ¹ and R ² are respectively H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl or heteroaryl.

G and L are H, F, or Cl, respectively, and one of G and L is Cl. Preferably, one of G and L is Cl, and the other is H.

R ⁵ to R ⁸ are each unsubstituted or substituted with at least one R ¹⁸ is C ₄ ~ C ₃₀ straight-chain, branched or cyclic alkyl, unsubstituted or substituted with at least one R ¹⁸ is C ₄ ~ C ₃₀ Alkenyl, or unsubstituted or substituted with at least one R ¹⁸ C ₄ ~C ₃₀ alkynyl; R ¹⁸ is halogen, ‒CN or ‒SiR ¹⁹ R ²⁰ R ²¹ ; R ¹⁹ to R ²¹ are each C ₁ to C ₃₀ alkyl.

Ar ¹ to Ar ⁶ are respectively an arylene group or a heteroarylene group.

R ⁰ is ‒NH‒, ‒NR ²² ‒, arylene or heteroarylene; R ²² is C ₁ ~C ₃₀ alkyl, aryl or heteroaryl. Preferably, R ⁰ is ‒NR ²² ‒, a substituted or unsubstituted divalent phenyl group, a substituted or unsubstituted divalent thienyl group, or a substituted or unsubstituted divalent pyrazinyl group.

> Example 1>

Preparation of copolymer

The copolymer of Example 1 contains the structure shown below, wherein X is F or Cl.

實施例 1

Example 1

化合物 1 化合物 2 在氮氣下將化合物1 (10 mmol)和氫硼化鈉(NaBH₄ )(25 mmol)入料於250 mL反應瓶中，加入100 mL的無水乙醇(EtOH)，加熱至78℃至攪拌1小時。接著，加入水並用二氯甲烷萃取及用無水硫酸鎂乾燥後，過濾去除固體。濾液濃縮去除溶劑，得到深咖啡色固體的化合物2 。 步驟 2( 製備化合物 4)

化合物 3 化合物 4 在氮氣下將化合物3 (12 mmol)入料於250 mL反應瓶中，加入150 mL的無水四氫呋喃(THF)，降至0℃。接著，逐滴加入2.5 M的正丁基鋰(n-BuLi)的正己烷溶液(12mmol)，維持0^o C 1小時，再逐滴加入3-(溴甲基)庚烷[3-(bromomethyl)heptane](10 mmol)，回室溫後攪拌3小時。最後，加入水並用正庚烷萃取及用無水硫酸鎂乾燥，過濾去除固體，濾液濃縮去除溶劑。以矽膠管柱層析(正庚烷)進行純化得到淡黃色液體的化合物4 。 步驟 3( 製備化合物 5)

化合物 4 化合物 5 在氮氣下將化合物4 (21 mmol)和三氯化鋁(AlCl₃ )(21 mmol)入料於250 mL反應瓶中。接著，加入100 mL的無水二氯甲烷(DCM)，逐滴加入草醯氯[(COCl)₂ ](10 mmol)，攪拌1小時。最後，加入水並用二氯甲烷萃取及用無水硫酸鎂乾燥。過濾去除固體，濾液濃縮去除溶劑，以矽膠管柱層析(正庚烷/二氯甲烷)進行純化得到黃色固體的化合物5 。 步驟 4( 製備化合物 6)

化合物 2 化合物 5 化合物 6 在氮氣下將化合物2 (11.5 mmol)和化合物5 (10 mmol)入料於250 mL反應瓶中。接著，加入100 mL的無水醋酸(AcOH)，加熱至90℃ 1小時，濃縮去除溶劑。最後，以矽膠管柱層析(正庚烷/二氯甲烷)進行純化得到黃色固體的化合物6 。 步驟 5( 製備化合物 7)

化合物 6 化合物 7 在氮氣下將化合物6 (10 mmol)、2-三丁基錫烷基噻吩(21 mmol)、 三(2-呋喃基)膦[(o-toly)₃ P](0.3 mol)、三(二亞苄基丙酮)二鈀[Pd₂ (dba)₃ ](1.2 mol)入料於250 mL反應瓶中。接著，加入150 mL的無水甲苯(PhMe)，在110℃下攪拌2小時。最後，濃縮去除溶劑，以矽膠管柱層析(正庚烷/二氯甲烷)進行純化得到橘色固體的化合物7 。 步驟 6( 製備化合物 8)

化合物 7 化合物 8 在氮氣下將化合物7 (10 mmol)、N-溴代丁二醯亞胺(NBS)(21 mmol)入料於250 mL反應瓶中。接著，加入100 mL的無水四氫呋喃(THF)，在室溫下攪拌6小時。最後，濃縮去除溶劑，以矽膠管柱層析(正庚烷/二氯甲烷)進行純化得到紅色固體的化合物8 。 步驟 7( 製備實施例 1)

化合物 9 化合物 8 實施例 1 在氮氣下將化合物8 (1 mmol)、化合物9 (1 mmol)、三(2-呋喃基)膦[(o-toly)₃ P](0.12 mol)、三(二亞苄基丙酮)二鈀[Pd₂ (dba)₃ ](0.03 mol)入料於100 mL反應瓶中。接著，加入40 mL的無水氯苯(PhCl)，在130℃下攪拌1小時，將反應冷卻至室溫後將反應瓶的內容物倒至甲醇中析出固體。過濾收集沉澱物，並將該固體依序以甲醇、丙酮和氯仿進行索氏(Soxhlet)萃取。最後，將氯仿殘液倒至甲醇中再沉澱，再過濾收集沉澱物，以真空乾燥得到紅黑色的共聚物(實施例1 )。The copolymer of Example 1 was prepared according to the following steps 1-7. It should be noted that X in all chemical formulas of steps 1 to 7 is F or Cl. Step 1 ( Preparation of Compound 2)

Compound 1 Compound 2 Under nitrogen, put compound 1 (10 mmol) and sodium borohydride (NaBH ₄ ) (25 mmol) into a 250 mL reaction flask, add 100 mL of absolute ethanol (EtOH), and heat to 78°C Stir for 1 hour. Then, after adding water and extracting with dichloromethane and drying with anhydrous magnesium sulfate, the solid was removed by filtration. The filtrate was concentrated to remove the solvent, and compound 2 was obtained as a dark brown solid. Step 2 ( Preparation of compound 4)

Compound 3 and Compound 4 Under nitrogen, compound 3 (12 mmol) was charged into a 250 mL reaction flask, 150 mL of anhydrous tetrahydrofuran (THF) was added, and the temperature was reduced to 0°C. Then, 2.5 M n-BuLi (n-BuLi) n-hexane solution (12 mmol) was ^{added dropwise, maintained at 0 o} C for 1 hour, and then 3-(bromomethyl)heptane [3-(bromomethyl) was added dropwise )heptane] (10 mmol), return to room temperature and stir for 3 hours. Finally, water was added and extracted with n-heptane and dried with anhydrous magnesium sulfate. The solid was removed by filtration, and the filtrate was concentrated to remove the solvent. Purified by silica gel column chromatography (n-heptane) to obtain compound 4 as a pale yellow liquid. Step 3 ( Preparation of Compound 5)

Compound 4 Compound 5 Compound 4 (21 mmol) and aluminum trichloride (AlCl ₃ ) (21 mmol) were fed into a 250 mL reaction flask under nitrogen. Next, 100 mL of anhydrous dichloromethane (DCM) was added, oxalic chloride [(COCl) ₂ ] (10 mmol) was added dropwise, and the mixture was stirred for 1 hour. Finally, water was added and extracted with dichloromethane and dried with anhydrous magnesium sulfate. The solid was removed by filtration, the filtrate was concentrated to remove the solvent, and purified by silica gel column chromatography (n-heptane/dichloromethane) to obtain compound 5 as a yellow solid. Step 4 ( Preparation of Compound 6)

Compound 2 Compound 5 Compound 6 Compound 2 (11.5 mmol) and Compound 5 (10 mmol) were fed into a 250 mL reaction flask under nitrogen. Then, 100 mL of anhydrous acetic acid (AcOH) was added, heated to 90° C. for 1 hour, and concentrated to remove the solvent. Finally, it was purified by silica gel column chromatography (n-heptane/dichloromethane) to obtain compound 6 as a yellow solid. Step 5 ( Preparation of compound 7)

Compound 6 Compound 7 Compound 6 (10 mmol), 2-tributylstannylthiophene (21 mmol), tris(2-furyl)phosphine [(o-toly) ₃ P] (0.3 mol), three (Dibenzylideneacetone)dipalladium [Pd ₂ (dba) ₃ ] (1.2 mol) was charged into a 250 mL reaction flask. Next, 150 mL of anhydrous toluene (PhMe) was added, and the mixture was stirred at 110°C for 2 hours. Finally, it was concentrated to remove the solvent, and purified by silica gel column chromatography (n-heptane/dichloromethane) to obtain compound 7 as an orange solid. Step 6 ( Preparation of Compound 8)

Compound 7 and Compound 8 Compound 7 (10 mmol) and N-bromosuccinimide (NBS) (21 mmol) were charged into a 250 mL reaction flask under nitrogen. Next, 100 mL of anhydrous tetrahydrofuran (THF) was added, and the mixture was stirred at room temperature for 6 hours. Finally, it was concentrated to remove the solvent, and purified by silica gel column chromatography (n-heptane/dichloromethane) to obtain compound 8 as a red solid. Step 7 ( Preparation Example 1)

Compound 9 Compound 8 Example 1 Under nitrogen, compound 8 (1 mmol), compound 9 (1 mmol), tris(2-furyl)phosphine [(o-toly) ₃ P] (0.12 mol), tris (two Benzylacetone) two palladium [Pd ₂ (dba) ₃ ] (0.03 mol) was charged into a 100 mL reaction flask. Next, 40 mL of anhydrous chlorobenzene (PhCl) was added and stirred at 130°C for 1 hour. After the reaction was cooled to room temperature, the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration, and the solid was subjected to Soxhlet extraction with methanol, acetone, and chloroform in this order. Finally, the chloroform residue was poured into methanol for reprecipitation, and then the precipitate was collected by filtration, and dried in a vacuum to obtain a red-black copolymer (Example 1 ).

> Example 2>

Preparation of copolymer

The copolymer of Example 2 contains the structure shown below, wherein X is F or Cl.

實施例 2

Example 2

化合物 10 化合物 8 實施例 2 在氮氣下將化合物8 (1 mmol)、化合物10 (1 mmol) 、三(2-呋喃基)膦[(o-toly)₃ P](0.12 mol)、三(二亞苄基丙酮)二鈀[Pd₂ (dba)₃ ](0.03 mol)入料於100 mL反應瓶中。接著，加入35 mL的無水氯苯(PhCl)，在130℃下攪拌1小時。將反應冷卻至室溫後將反應瓶的內容物倒至甲醇中析出固體。過濾收集沉澱物，並將該固體依序以甲醇、丙酮和氯仿進行索氏(Soxhlet)萃取。最後，將氯仿殘液倒至甲醇中再沉澱，再過濾收集沉澱物，以真空乾燥得到共聚物(實施例2 )。The steps of the embodiment 2 are similar to those of the embodiment 1, the difference is that the step 7 of the embodiment 1 is replaced by the following step 7'in the embodiment 2. It should be noted that X in all chemical formulas in step 7'is F or Cl. Step 7'( Preparation Example 2)

Compound 10 Compound 8 Example 2 Under nitrogen, compound 8 (1 mmol), compound 10 (1 mmol), tris (2-furyl) phosphine [(o-toly) ₃ P] (0.12 mol), tris (two Benzylacetone) two palladium [Pd ₂ (dba) ₃ ] (0.03 mol) was charged into a 100 mL reaction flask. Next, 35 mL of anhydrous chlorobenzene (PhCl) was added, and the mixture was stirred at 130°C for 1 hour. After the reaction was cooled to room temperature, the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration, and the solid was subjected to Soxhlet extraction with methanol, acetone, and chloroform in this order. Finally, the chloroform residue was poured into methanol for reprecipitation, and then the precipitate was collected by filtration and dried in a vacuum to obtain a copolymer (Example 2 ).

> Example 3>

Preparation of copolymer

The copolymer of Example 3 contains the structure shown below, wherein X is F or Cl.

實施例 3

Example 3

化合物 11 化合物 8 實施例 3 在氮氣下將化合物8 (1 mmol)、化合物11 (1 mmol) 、三(2-呋喃基)膦[(o-toly)3P](0.12 mol)、三(二亞苄基丙酮)二鈀[Pd₂ (dba)₃ ] (0.03 mol)入料於100 mL反應瓶中。接著，加入35 mL的無水氯苯(PhCl)，在130℃下攪拌1小時，將反應冷卻至室溫後將反應瓶的內容物倒至甲醇中析出固體。過濾收集沉澱物，並將該固體依序以甲醇、丙酮和氯仿進行索氏(Soxhlet)萃取。最後，將氯仿殘液倒至甲醇中再沉澱，再過濾收集沉澱物，以真空乾燥得到共聚物(實施例3 )。The steps of embodiment 3 are similar to those of embodiment 1, the difference lies in that, embodiment 3 replaces step 7 of embodiment 1 with the following step 7''. It should be noted that X in all chemical formulas in step 7′′ is F or Cl. Step 7'' ( Preparation Example 3)

Compound 11 Compound 8 Example 3 Compound 8 (1 mmol), compound 11 (1 mmol), tris(2-furyl)phosphine [(o-toly)3P] (0.12 mol), tris(diethylene) were added under nitrogen. Benzylacetone) two palladium [Pd ₂ (dba) ₃ ] (0.03 mol) was charged into a 100 mL reaction flask. Next, 35 mL of anhydrous chlorobenzene (PhCl) was added and stirred at 130°C for 1 hour. After the reaction was cooled to room temperature, the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration, and the solid was subjected to Soxhlet extraction with methanol, acetone, and chloroform in this order. Finally, the chloroform residue was poured into methanol for reprecipitation, and the precipitate was collected by filtration, and dried in a vacuum to obtain a copolymer (Example 3 ).

The number of the copolymer represented when X in the copolymers of Examples 1 to 2 is F or Cl, respectively, is summarized in Table 1 below. Table 1 Example X Copolymer number 1 Cl Copolymer 1 1 F Copolymer 2 2 Cl Copolymer 3 2 F Copolymer 4

> Example 4>

Preparation of copolymer

實施例 4 The copolymer of Example 4 includes the structure shown below, wherein a and b are both greater than 0 and less than 1, and the sum of a and b is 1, and X is F or Cl.

Example 4

化合物 14 的製備方法 在氮氣下將化合物12 (1 mmol)入料於100 mL反應瓶中，加入15 mL的無水甲苯(PhMe)和0.3 mL的無水二甲基醯胺(DMF)，逐滴加入1.5 mL的乙二醯氯(COCl)₂ ，在66℃下攪拌2小時。接著，抽去所有溶劑，加入三氯化鋁(AlCl₃ )(1.5 mmol)，加入20 mL的無水二氯甲烷(DCM)，逐滴加入化合物13 (1 mmol)，攪拌1小時，將反應倒入冰中。最後，用二氯甲烷(DCM)進行萃取三次，有機層加入硫酸鎂除水，經濃縮後，再以甲苯和甲醇進行重結晶得到淡黃色固體的化合物14 。 化合物 15 的製備方法 在氮氣下將化合物14 (1 mmol)、2-三丁基錫烷基噻吩(2.1 mmol)、三(2-呋喃基)膦[(o-toly)₃ P](0.03 mol)、三(二亞苄基丙酮)二鈀[Pd₂ (dba)₃ ](0.12 mol)入料於100 mL反應瓶中。接著，加入15 mL的無水甲苯(PhMe)，在110℃下攪拌2小時，濃縮去除溶劑。最後，以甲苯和甲醇進行重結晶得到黃色固體的化合物15 。 化合物 16 的製備方法 在氮氣下將化合物15 (1 mmol) 、N-溴代丁二醯亞胺(NBS)(2.1 mmol)入料於100 mL反應瓶中，加入15 mL的無水四氫呋喃(THF)，在室溫下攪拌6小時，加入甲醇析出固體。最後，過濾並用甲醇沖洗，得到深黃色固體的化合物16 。 [反應式ii]

實施例 4 的製備方法 在氮氣下將化合物10 (0.50 mmol)、化合物8 (0.25 mmol)、化合物16 (0.25 mmol)、三(2-呋喃基)膦[(o-toly)₃ P](0.08 mol)、三(二亞苄基丙酮)二鈀[Pd₂ (dba)₃ ](0.02 mol)入料於100 mL反應瓶中。接著，加入35 mL的無水氯苯(PhCl)，在130℃下攪拌4小時，將反應冷卻至室溫後將反應瓶的內容物倒至甲醇中析出固體。過濾收集沉澱物，並將該固體依序以甲醇、丙酮和氯仿進行索氏(Soxhlet)萃取。最後，將氯仿殘液倒至甲醇中再沉澱，再過濾收集沉澱物，以真空乾燥得到共聚物(實施例4 )。The copolymer of Example 4 was prepared according to the following reaction formulas i and ii and the following steps. It should be noted that in reaction formula ii, a and b are both greater than 0 and less than 1, and the sum of a and b is 1, and X is F or Cl. [Reaction formula i]

Preparation method of compound 14 Put compound 12 (1 mmol) into a 100 mL reaction flask under nitrogen, add 15 mL of anhydrous toluene (PhMe) and 0.3 mL of anhydrous dimethylamide (DMF), add dropwise 1.5 mL of ethylenedichloride (COCl) ₂ , and stir at 66°C for 2 hours. Then, all the solvents were removed, aluminum trichloride (AlCl ₃ ) (1.5 mmol) was added, 20 mL of anhydrous dichloromethane (DCM) was added, compound 13 (1 mmol) was added dropwise, stirred for 1 hour, and the reaction was poured Into the ice. Finally, it was extracted three times with dichloromethane (DCM), and the organic layer was added with magnesium sulfate to remove water. After concentration, it was recrystallized with toluene and methanol to obtain compound 14 as a pale yellow solid. Preparation method of compound 15 under nitrogen, compound 14 (1 mmol), 2-tributylstannylthiophene (2.1 mmol), tris(2-furyl)phosphine [(o-toly) ₃ P] (0.03 mol), Tris(dibenzylideneacetone)dipalladium [Pd ₂ (dba) ₃ ] (0.12 mol) was charged into a 100 mL reaction flask. Next, 15 mL of anhydrous toluene (PhMe) was added, stirred at 110°C for 2 hours, and concentrated to remove the solvent. Finally, it was recrystallized from toluene and methanol to obtain compound 15 as a yellow solid. Preparation method of compound 16 Put compound 15 (1 mmol) and N-bromosuccinimide (NBS) (2.1 mmol) into a 100 mL reaction flask under nitrogen, and add 15 mL of anhydrous tetrahydrofuran (THF) , Stir at room temperature for 6 hours, add methanol to precipitate a solid. Finally, it was filtered and washed with methanol to obtain compound 16 as a dark yellow solid. [Reaction formula ii]

The preparation method of Example 4 Compound 10 (0.50 mmol), compound 8 (0.25 mmol), compound 16 (0.25 mmol), tris(2-furyl)phosphine [(o-toly) ₃ P](0.08 mol), three (dibenzylideneacetone) two palladium [Pd ₂ (dba) ₃ ] (0.02 mol) were charged into a 100 mL reaction flask. Next, 35 mL of anhydrous chlorobenzene (PhCl) was added and stirred at 130°C for 4 hours. After the reaction was cooled to room temperature, the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration, and the solid was subjected to Soxhlet extraction with methanol, acetone, and chloroform in this order. Finally, the chloroform residue was poured into methanol for reprecipitation, and then the precipitate was collected by filtration, and dried in vacuum to obtain a copolymer (Example 4 ).

The copolymer numbers represented when X in the copolymer of Example 4 is Cl and a and b are in different ratios are summarized in Table 2 below. Table 2 Example X a b Copolymer number 4 Cl 0.2 0.8 Copolymer 5 4 Cl 0.5 0.5 Copolymer 6 4 Cl 0.8 0.2 Copolymer 7

> UV - Visible light (UV-Vis) Absorption spectrum >

Firstly, Fig. 1A and Fig. 1B are the ultraviolet-visible light absorption spectra measured by the instrument after dissolving copolymers 1~4 and 5~7 in chloroform, respectively; Fig. 2A and Fig. 2B show the copolymer 1 After ~4 and 5~7 are dissolved in chloroform, they are coated on a transparent glass slide and dried to form a solid film. The UV-visible light absorption spectrum measured by the instrument is used.

Referring to the spectrograms of Figures 1A, 1B, 2A, and 2B, the aforementioned copolymers 1 to 7 have a wide absorption wavelength distribution and high absorption in the ultraviolet-visible region, so the aforementioned copolymers can be used as a wide band gap. Electron donor material.

> Organic photoelectric element structure >

The organic photoelectric element of the present invention includes, but is not limited to, organic light-emitting diodes, organic thin film transistors, organic photovoltaic elements (OPV), and organic photodetectors (organic photodetectors). , OPD), the present invention takes organic photovoltaic elements (OPV) as an example.

Fig. 3 is a cross-sectional view of the first structure of the organic photovoltaic element used in the present invention. The organic photovoltaic device includes a substrate 70, a first electrode 80 laminated on the substrate 70, an organic semiconductor layer 90 laminated on the first electrode 80, and a second electrode laminated on the organic semiconductor layer 90 100. Wherein, the organic semiconductor layer 90 includes an electron transport layer 91 laminated on the first electrode 80, an active layer 92 laminated on the electron transport layer 91, and a hole transport layer laminated on the active layer 92 93. Therefore, the second electrode 100 is laminated on the hole transport layer 93.

Fig. 4 is a cross-sectional view of the second structure of the organic photovoltaic element used in the present invention. The organic photovoltaic device includes a substrate 70, a first electrode 80 laminated on the substrate 70, an organic semiconductor layer 90 laminated on the first electrode 80, and a second electrode laminated on the organic semiconductor layer 90 100. Wherein, the organic semiconductor layer 90 includes a hole transport layer 93 laminated on the first electrode 80, an active layer 92 laminated on the hole transport layer 93, and an electron transport layer laminated on the active layer 92 Layer 91. Therefore, the second electrode 100 is laminated on the electron transport layer 91.

For the convenience of description and understanding, the following uses the structure of the organic photovoltaic element in FIG. 3 as an implementation manner of an application example.

> Application example 1~14>

Preparation of organic photovoltaic elements (OPV)

According to the active layer materials (copolymer and electron acceptor materials) listed in Table 4 below, and the following methods, the organic photovoltaic elements of Application Examples 1 to 14 were prepared. Table 4 Application example Active layer material Copolymer Electron acceptor material 1 Copolymer 1 Compound 17 2 Copolymer 1 Compound 18 3 Copolymer 2 Compound 17 4 Copolymer 2 Compound 18 5 Copolymer 3 Compound 17 6 Copolymer 3 Compound 18 7 Copolymer 4 Compound 17 8 Copolymer 4 Compound 18 9 Copolymer 5 Compound 17 + Compound 19 10 Copolymer 6 Compound 17 + Compound 19 11 Copolymer 7 Compound 17 + Compound 19 12 Copolymer 5 Compound 18 + Compound 19 13 Copolymer 6 Compound 18 + Compound 19 14 Copolymer 7 Compound 18 + Compound 19

Before preparing the organic photovoltaic element, the patterned ITO glass substrate (12 Ω/□) was washed in the ultrasonic oscillation tank with detergent, deionized water, acetone and isopropanol for 10 minutes respectively. After the ITO glass substrate was cleaned by ultrasonic vibration, the surface treatment was performed in a UV-ozone cleaning machine for 30 minutes. The glass substrate is the aforementioned substrate 70, and the ITO is the aforementioned first electrode 80, which is the anode in the structure of FIG. 3.

The zinc acetate [Zn(OAc) ₂ ] solution was spin-coated on the ITO glass substrate and baked at 170° C. for 30 minutes to form a ZnO layer (zinc oxide layer), which is the aforementioned electron transport layer 91.

Use the copolymers listed in Application Examples 1 to 8 in Table 4 as electron donor materials and mix them with non-fullerene electron acceptor materials (compounds 17 or 18) at a weight ratio of 1:1 , Prepare the active layer solution with chlorobenzene as the solvent. Next, spin-coated the active layer solution on the aforementioned ZnO layer (electron transport layer 91), and baked at 120°C under nitrogen for 10 minutes to form the aforementioned active layer on the ZnO layer (electron transport layer 91) 92. Then, it is sent into a vacuum chamber and heated to deposit a molybdenum trioxide (MoO ₃ ) metal oxide (about 4 nm) to form the aforementioned hole transport layer 93 on the active layer 92. Then, Ag metal (about 100 nm) is heated and deposited as the aforementioned second electrode 100, which is the cathode in the structure of FIG. 3.

化合物 17

化合物 18 The electron acceptor materials used in Application Examples 1 to 8 are the following compound 17 or compound 18.

Compound 17

Compound 18

According to the application examples 9 to 14 listed in Table 4, the copolymer is used as the electron donor material, and the weight ratio with the non-fullerene electron acceptor material (compound 17 or 18) and compound 19 is 1:1: After mixing in a ratio of 0.4, chlorobenzene was used as a solvent to prepare an active layer solution. Next, spin-coated the active layer solution on the aforementioned ZnO layer (electron transport layer 91), and baked at 120°C under nitrogen for 10 minutes to form the aforementioned active layer on the ZnO layer (electron transport layer 91) 92. Then, it is sent into a vacuum chamber and heated to deposit a molybdenum trioxide (MoO ₃ ) metal oxide (about 4 nm) on the active layer 92 to form the aforementioned hole transport layer 93. Then, Ag metal (about 100 nm) is heated and deposited as the aforementioned second electrode 100, which is the cathode in the structure of FIG. 3.

化合物 19 The electron acceptor materials used in Application Examples 9-14 are the aforementioned compound 17, compound 18 and the following compound 19.

Compound 19

> Electrical analysis of organic photovoltaic elements >

The measurement area of the organic photovoltaic element is defined as 0.04 cm ² through the metal mask. Keithley 2400 is used as a power supply, controlled by Lab-View program, under the illumination of AM1.5G simulated sunlight (SAN-EI XES-40S3) with an ^{illuminance of 100 mW/cm 2 to measure the electrical properties of the component, and use a computer program} Record, the voltage-current curves obtained by applying the organic photovoltaic elements of Examples 1-14 are shown in Figure 5A and Figure 5B, respectively.

> Analysis of Energy Conversion Efficiency (PCE) of Organic Photovoltaic Components> Table 5 Application example Active layer material Voc (V) Jsc (mA/cm ₂ ) FF (%) PCE (%) Copolymer Electron acceptor material 1 Copolymer 1 Compound 17 0.810 23.02 68 12.7 2 Copolymer 1 Compound 18 0.798 24.51 71 13.8 3 Copolymer 2 Compound 17 0.775 24.62 68 13.0 4 Copolymer 2 Compound 18 0.778 24.82 65 12.5 5 Copolymer 3 Compound 17 0.830 23.22 69 13.3 6 Copolymer 3 Compound 18 0.840 24.27 70 14.2 7 Copolymer 4 Compound 17 0.820 23.97 68 13.3 8 Copolymer 4 Compound 18 0.830 22.94 72 13.7 9 Copolymer 5 Compound 17+ Compound 19 0.838 17.15 65 9.4 10 Copolymer 6 Compound 17+ Compound 19 0.828 21.87 69 12.5 11 Copolymer 7 Compound 17+ Compound 19 0.815 23.83 73 14.2 12 Copolymer 5 Compound 18+ Compound 19 0.840 24.00 75 15.2 13 Copolymer 6 Compound 18+ Compound 19 0.840 22.91 69 13.3 14 Copolymer 7 Compound 18+ Compound 19 0.835 24.16 73 14.7

In Table 5, Voc represents open voltage, Jsc represents short-circuit current, FF represents fill factor, and PCE represents energy conversion efficiency. The open circuit voltage and the short circuit current are the intercepts of the voltage-current density curve on the X-axis and the Y-axis. When these two values increase, the efficiency of the organic photovoltaic device is better improved. In addition, the fill factor is the value obtained by dividing the area that can be drawn in the curve by the product of the short-circuit current and the open-circuit voltage. When the three values of open circuit voltage, short circuit current, and fill factor are divided by the irradiated light, the energy conversion efficiency can be obtained, and the higher value of the energy conversion efficiency is better.

From the results in Table 5, it can be found that the organic photovoltaic cells of Application Examples 1 to 14 have good energy conversion efficiency (PCE). Therefore, from the foregoing results, it can be seen that the copolymer of the present invention can be used as an electron donor material. Improve the absorption in the visible light region to improve the energy level matching with non-fullerene electron acceptor materials, so it can effectively improve the energy conversion efficiency (PCE) of organic photovoltaic cells. In particular, when changing different electron donor materials, the copolymer 5 of Application Example 12 performs best.

However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, all simple equivalent changes and modifications made in accordance with the scope of the patent application of the present invention and the content of the patent specification still belong to This invention patent covers the scope.

70: substrate 80: first electrode 90: organic semiconductor layer 91: electron transport layer 92: active layer 93: hole transport layer 100: second electrode

Other features and effects of the present invention will be clearly presented in the embodiments with reference to the drawings, in which: Figures 1A and 1B are respectively a spectrogram showing the ultraviolet-visible light absorption spectra of copolymers 1-7 in solution; Figures 2A and 2B are respectively a spectrum diagram illustrating the ultraviolet-visible light absorption spectra of the copolymers 1-7 in the solid-state film formation; Figure 3 is a schematic cross-sectional view illustrating the first structure of the organic photovoltaic element of the present invention; 4 is a schematic cross-sectional view illustrating the second structure of the organic photovoltaic device of the present invention; and Figures 5A and 5B are graphs respectively illustrating the voltage-current density of the organic photovoltaic elements of application examples 1-14.

Claims (15)

A copolymer comprising the structure represented by the following chemical formula (I): [Chemical formula (I)]

Where W is

, Y is

, Z is

, W, Y, and Z are different from each other; a, b, and c are all real numbers, and 0≦a≦1, 0≦b≦1, 0≦c≦1, and the sum of a, b, and c is 1; p , P', q, q', r and r'are 0, 1 or 2 respectively; A ¹ , A ² and A ³ are groups represented by the following formula (1) or formula (2), and at least one ^{A 1} , A ² or A ³ in the chemical formula (I) is a group represented by the formula (1); [formula (1)]

[Equation (2)]

R ¹ and R ² are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl or heteroaryl, respectively; G and L are H, F or Cl, and one of G and L is Cl; R ⁵ to R ⁸ are respectively unsubstituted or substituted with at least one R ¹⁸ C ₄ to C ₃₀ linear, branched or cyclic alkyl, unsubstituted unsubstituted or substituted with at least one R ¹⁸ is C ₄ ~ C ₃₀ alkenyl group, or unsubstituted or substituted at least by one R ¹⁸ is C ₄ ~ C ₃₀ alkynyl group; R ¹⁸ is halogen, -CN, or -SiR ¹⁹ R ²⁰ R ²¹ ; R ¹⁹ to R ²¹ are C ₁ ~C ₃₀ alkyl groups; R ⁰ is ‒NH‒, ‒NR ²² ‒, arylene or heteroarylene; R ²² is C ₁ ~C ₃₀ alkyl, Aryl or heteroaryl; and Ar ¹ to Ar ⁹ are arylene or heteroarylene, respectively. The copolymer according to claim 1, wherein Ar ¹ , Ar ⁴ and Ar ⁷ are respectively

, And R ³ and R ⁴ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl, heteroaryl, or ‒Si(R ⁹ ) ₃ , and R ⁹ has the same definition as ^{R 5.} The copolymer according to claim 2, wherein the aryl groups in ^{R 1} to R ^{4 are}

, And n ₁ is 1, 2, 3, 4 or 5; and R ¹⁰ is H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ or ‒Si (R ⁹ ) ₃ . The copolymer according to claim 2, wherein the heteroaryl group in ^{R 1} to R ^{4 is}

, And n ₂ is 1, 2, 3, 4, or 5; and R ¹¹ to R ¹³ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR, respectively ⁸ or ‒Si(R ⁹ ) ₃ . The copolymer according to claim 1, wherein Ar ² , Ar ³ , Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ are respectively

or

, And n ₃ and n ₄ are 1, 2 or 3 respectively; and R ¹⁴ to R ¹⁷ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR, respectively ^8. Aryl or heteroaryl. The copolymer according to claim 1, wherein R ⁰ is ‒NR ²² ‒, a substituted or unsubstituted divalent phenyl group, a substituted or unsubstituted divalent thienyl group, or a substituted or unsubstituted divalent thiophene group Substituted divalent pyrazinyl. A copolymer comprising the structure shown in the following chemical formula (II): [Chemical formula (II)]

Wherein, p and p'are 0, 1 or 2 respectively; A ¹ is a group represented by the following formula (1); [Formula (1)]

R ¹ is the ^{same as R 2} and are respectively H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl or heteroaryl; G and L respectively Is H, F or Cl, and one of G and L is Cl; Ar ² and Ar ³ are respectively arylene or heteroarylene; Ar ¹ is

; R ³ and R ⁴ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl, ‒Si(R ⁹ ) ₃ or

; N ₂ is 1, 2, 3, 4 or 5; R ¹¹ to R ¹³ are respectively H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ or ‒Si(R ⁹ ) ₃ ; R ⁵ to R ⁹ are C ₄ to C ₃₀ linear, branched or cyclic alkyl that is unsubstituted or substituted with at least one R ^{18, unsubstituted or substituted with at least one R 18} substituted C ₄ ~C ₃₀ alkenyl, or unsubstituted or substituted with at least one R ¹⁸ C ₄ ~C ₃₀ alkynyl; R ¹⁸ is halogen, ‒CN or ‒SiR ¹⁹ R ²⁰ R ²¹ ; and R ¹⁹ To R ²¹ are C ₁ to C ₃₀ alkyl groups, respectively. The copolymer according to claim 7, wherein Ar ² and Ar ³ are respectively

or

, And n ₃ and n ₄ are 1, 2 or 3 respectively; and R ¹⁴ to R ¹⁷ are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR, respectively ^8. Aryl or heteroaryl. The copolymer according to claim 8, wherein Ar ² and Ar ³ are respectively

. The copolymer according to claim 7, wherein Ar ¹ is

,

or

. A copolymer comprising the structure represented by the following chemical formula (III): [Chemical formula (III)]

Where W is

, Y is

, W and Y are different from each other; a and b are real numbers, and 0>a>1, 0>b>1, and the sum of a and b is 1; p, p′, q, and q′ are 0, 1 or 2; A ¹ and A ² are groups represented by the following formula (1) or formula (2) respectively, and ^{at least one of A 1} and A ^{2 is} a group represented by formula (1); [formula( 1)]

[Equation (2)]

R ¹ and R ² are H, F, Cl, R ⁵ , ‒CN, ‒OR ⁶ , ‒SR ⁷ , ‒C(=O)OR ⁸ , aryl or heteroaryl, respectively; G and L are H, F or Cl, and one of G and L is Cl; R ⁵ to R ⁸ are respectively unsubstituted or substituted with at least one R ¹⁸ C ₄ to C ₃₀ linear, branched or cyclic alkyl, unsubstituted unsubstituted or substituted with at least one R ¹⁸ is C ₄ ~ C ₃₀ alkenyl group, or unsubstituted or substituted at least by one R ¹⁸ is C ₄ ~ C ₃₀ alkynyl group; R ¹⁸ is halogen, -CN, or -SiR ¹⁹ R ²⁰ R ²¹ ; R ¹⁹ to R ²¹ are C ₁ ~C ₃₀ alkyl groups; R ⁰ is ‒NH‒, ‒NR ²² ‒, arylene or heteroarylene; R ²² is C ₁ ~C ₃₀ alkyl, Aryl or heteroaryl; and Ar ¹ to Ar ⁶ are arylene or heteroarylene, respectively. The copolymer according to claim 11, wherein R ⁰ is ‒NR ²² ‒, a substituted or unsubstituted divalent phenyl group, a substituted or unsubstituted divalent thienyl group, or a substituted or unsubstituted divalent thiophene group Substituted divalent pyrazinyl. An organic photovoltaic element comprising the copolymer according to any one of claims 1, 7 or 11. The organic photovoltaic element according to claim 13, wherein the organic photovoltaic element comprises a substrate, a first electrode laminated on the substrate, an electron transport layer laminated on the first electrode, and an electron transport layer laminated on the electron An active layer above the transmission layer, a hole transmission layer laminated on the active layer, and a second electrode laminated on the hole transmission layer, and the active layer includes the copolymer. The organic photovoltaic element according to claim 13, wherein the organic photovoltaic element includes a substrate, a first electrode layered on the substrate, a hole transport layer layered on the first electrode, and a hole transport layer layered on the first electrode. An active layer above the hole transport layer, an electron transport layer stacked above the active layer, and a second electrode stacked above the electron transport layer, and the active layer includes the copolymer.

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