TWI717153B - Non-fullerene electron acceptor materials and organic photovoltaic cells - Google Patents

Non-fullerene electron acceptor materials and organic photovoltaic cells Download PDF

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TWI717153B
TWI717153B TW108146012A TW108146012A TWI717153B TW I717153 B TWI717153 B TW I717153B TW 108146012 A TW108146012 A TW 108146012A TW 108146012 A TW108146012 A TW 108146012A TW I717153 B TWI717153 B TW I717153B
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electron acceptor
alkyl
acceptor material
fullerene electron
fullerene
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黃懿萱
張純鳳
何嘉興
施宏旻
柯崇文
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位速科技股份有限公司
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Abstract

一種如式(I)所示的非富勒烯電子受體材料與一種主動層包括該非富勒烯電子受體材料的有機光伏電池。本發明的非富勒烯電子受體材料之吸收光譜範圍能有效延長至近紅外光區域，進而能有效捕獲更多近紅外光區的太陽光光子。A non-fullerene electron acceptor material represented by formula (I) and an organic photovoltaic cell in which an active layer includes the non-fullerene electron acceptor material. The absorption spectrum range of the non-fullerene electron acceptor material of the present invention can be effectively extended to the near-infrared light region, and can effectively capture more solar photons in the near-infrared light region.

Description

非富勒烯電子受體材料與有機光伏電池Non-fullerene electron acceptor materials and organic photovoltaic cells

本發明是有關於一種非富勒烯電子受體材料與一種主動層包括前述非富勒烯電子受體材料的有機光伏電池，特別是指一種具有強拉電子結構之苯并硒二唑(benzoselenadiazole)衍生物的非富勒烯電子受體材料與一種主動層包括前述非富勒烯電子受體材料的有機光伏電池。The present invention relates to an organic photovoltaic cell with a non-fullerene electron acceptor material and an active layer including the aforementioned non-fullerene electron acceptor material, in particular to a benzoselenadiazole (benzoselenadiazole) with a strong electronic structure. ) Derivative non-fullerene electron acceptor material and an organic photovoltaic cell in which the active layer includes the aforementioned non-fullerene electron acceptor material.

隨著時代的演進，如煤炭、石油、天然氣與核能等能源的消耗量日益漸增，能源危機也逐漸浮現。太陽能發電是一種可再生且可降低環境污染的環保發電方式。第一代的太陽能電池以矽晶(silicon)太陽能電池為大宗，其具有高光電轉換率。第二代的太陽能電池為薄膜(thin-film)型的碲化鎘(CdTe)太陽能電池，其原料毒性與製作方法對環境有較大的汙染。第三代的有機太陽能電池隨之蘊育而生，其包含了染料敏化電池(dye-sensitized solar cell；DSSC)、奈米結晶電池與有機光伏電池(organic photovoltaics；OPV)。與需利用真空製程鍍膜製作的無機材料相比，有機光伏電池可利用浸塗、旋轉塗布、狹縫式塗布、網版印刷與噴墨印刷等方法製作，更易實現低成本及大規模的生產。其中，新一代的有機光伏電池是以有機電子受體材料搭配共軛聚合物(電子給體材料)作為光伏主要吸收層(主動層)的材料。新一代的有機光伏電池具有幾項優點：(1)質量輕且製作成本低；(2)具有可撓性；(3)器件結構可設計性強；及 (4)適用於液相製程(即可大面積濕式塗布)。With the evolution of the times, the consumption of energy such as coal, oil, natural gas, and nuclear energy is increasing, and the energy crisis is gradually emerging. Solar power generation is an environmentally friendly power generation method that is renewable and can reduce environmental pollution. The first-generation solar cells are bulk silicon solar cells, which have a high photoelectric conversion rate. The second-generation solar cell is a thin-film cadmium telluride (CdTe) solar cell, and its raw material toxicity and manufacturing method have great environmental pollution. The third generation of organic solar cells followed up, including dye-sensitized solar cells (DSSC), nanocrystalline cells and organic photovoltaics (OPV). Compared with inorganic materials that need to be coated by a vacuum process, organic photovoltaic cells can be made by methods such as dip coating, spin coating, slit coating, screen printing, and inkjet printing, making it easier to achieve low-cost and large-scale production. Among them, the new generation of organic photovoltaic cells use organic electron acceptor materials with conjugated polymers (electron donor materials) as the main photovoltaic absorber layer (active layer) material. The new generation of organic photovoltaic cells has several advantages: (1) light weight and low production cost; (2) flexibility; (3) device structure can be designed; and (4) suitable for liquid-phase process (ie Large area wet coating).

新一代的有機光伏電池除了具有前述諸多優點外，其在主動層中的電子給體材料(共軛聚合物)之多樣性與發展使得有機光伏電池的能量轉換效率的提升已達到一定水準。然而，現有的有機電子受體材料大多以富勒烯衍生物(例如PC 60BM與PC 70BM)為主，其與電子給體材料(共軛聚合物)的搭配性易受到限制。此外，富勒烯衍生物本身亦有在光照下易二聚、加熱時易結晶、可見光區吸收弱、結構修飾與提純較不易、價格昂貴等缺點。因此，開發非富勒烯電子受體材料有存在的必要性。 In addition to the many advantages of the new generation of organic photovoltaic cells, the diversity and development of the electron donor materials (conjugated polymers) in the active layer have made the energy conversion efficiency of organic photovoltaic cells improved to a certain level. However, most of the existing organic electron acceptor materials are fullerene derivatives (such as PC 60 BM and PC 70 BM), and their compatibility with electron donor materials (conjugated polymers) is easily limited. In addition, the fullerene derivatives themselves also have shortcomings such as easy dimerization under light, easy crystallization when heated, weak absorption in the visible light region, difficult structure modification and purification, and high price. Therefore, it is necessary to develop non-fullerene electron acceptor materials.

CN109134513 A雖公開一種非富勒烯電子受體材料，能解決前述以富勒烯衍生物作為電子受體材料時所產生的缺點。然而，前述專利中的非富勒烯電子受體材料之吸收範圍仍有紅移的空間。Although CN109134513 A discloses a non-fullerene electron acceptor material, it can solve the aforementioned shortcomings when fullerene derivatives are used as electron acceptor materials. However, the absorption range of the non-fullerene electron acceptor material in the aforementioned patent still has room for red shift.

因此，如何改良現有的非富勒烯電子受體材料結構，使其吸收光譜紅移，進而能有效捕獲更多近紅外光區的太陽光光子，成為目前致力研究的目標。Therefore, how to improve the structure of the existing non-fullerene electron acceptor materials to make the absorption spectrum red shift, and then to effectively capture more solar photons in the near-infrared region, has become the goal of current research.

因此，本發明之第一目的，即在提供第一種非富勒烯電子受體材料，其相較於現有的非富勒烯電子受體材料，吸收光譜會紅移而能有效捕獲更多近紅外光區之太陽光光子。Therefore, the first objective of the present invention is to provide a first non-fullerene electron acceptor material, which, compared with the existing non-fullerene electron acceptor material, has a red shift in the absorption spectrum and can effectively capture more Solar photons in the near infrared region.

於是，本發明第一種的非富勒烯電子受體材料，如下式(I)所示： [式I]

Figure 02_image001
其中， R 1為C 1~C 30­烷基； A為
Figure 02_image003
、
Figure 02_image005
、
Figure 02_image007
、
Figure 02_image009
、
Figure 02_image011
、
Figure 02_image013
、
Figure 02_image015
、
Figure 02_image017
、
Figure 02_image019
、
Figure 02_image021
、
Figure 02_image023
、
Figure 02_image025
、
Figure 02_image027
或
Figure 02_image029
； R 2為氫、C 1~C 30烷基、C 1~C 30烷氧基、C 1~C 30烷基芳基 或C 1~C 30烷基雜芳基； B為
Figure 02_image031
、
Figure 02_image033
、
Figure 02_image035
、
Figure 02_image037
、
Figure 02_image039
或
Figure 02_image041
； R 3為氫、鹵素、C 1~C 30烷基或C 1~C 30烷氧基；及 R 4為氫或C 1~C 30烷基。 Therefore, the first non-fullerene electron acceptor material of the present invention is represented by the following formula (I): [Formula I]
Figure 02_image001
Wherein, R 1 is a C 1 ~C 30 alkyl group; A is
Figure 02_image003
,
Figure 02_image005
,
Figure 02_image007
,
Figure 02_image009
,
Figure 02_image011
,
Figure 02_image013
,
Figure 02_image015
,
Figure 02_image017
,
Figure 02_image019
,
Figure 02_image021
,
Figure 02_image023
,
Figure 02_image025
,
Figure 02_image027
or
Figure 02_image029
； R 2 is hydrogen, C 1 to C 30 alkyl, C 1 to C 30 alkoxy, C 1 to C 30 alkyl aryl, or C 1 to C 30 alkyl heteroaryl; B is
Figure 02_image031
,
Figure 02_image033
,
Figure 02_image035
,
Figure 02_image037
,
Figure 02_image039
or
Figure 02_image041
； R 3 is hydrogen, halogen, C 1 to C 30 alkyl or C 1 to C 30 alkoxy; and R 4 is hydrogen or C 1 to C 30 alkyl.

因此，本發明之第二目的，即在提供第二種由前述第一種非富勒烯電子受體材料所衍生的非富勒烯電子受體材料，其相較於現有的非富勒烯電子受體材料，吸收光譜同樣會紅移而能有效捕獲更多近紅外光區之太陽光光子。Therefore, the second objective of the present invention is to provide a second non-fullerene electron acceptor material derived from the aforementioned first non-fullerene electron acceptor material, which is compared with the existing non-fullerene electron acceptor material. For electron acceptor materials, the absorption spectrum will also be red-shifted and can effectively capture more solar photons in the near-infrared region.

於是，本發明第二種的非富勒烯電子受體材料是為高分子受體材料，包含下式(II)所示的重複單元：： [式II]

Figure 02_image043
其中， R 1為C 1~C 30­烷基； D為
Figure 02_image045
、
Figure 02_image047
、
Figure 02_image049
、
Figure 02_image051
、
Figure 02_image053
、
Figure 02_image055
、
Figure 02_image057
、
Figure 02_image059
、
Figure 02_image061
、
Figure 02_image063
、
Figure 02_image065
、
Figure 02_image067
、
Figure 02_image069
或
Figure 02_image071
； R 2為氫、C 1~C 30烷基、C 1~C 30烷氧基、C 1~C 30烷基芳基或C 1~C 30烷基雜芳基； E為
Figure 02_image073
、
Figure 02_image075
、
Figure 02_image077
、
Figure 02_image079
、
Figure 02_image081
或
Figure 02_image083
； R 3為氫、鹵素、C 1~C 30烷基或C 1~C 30烷氧基； L為
Figure 02_image085
、
Figure 02_image087
、
Figure 02_image089
、
Figure 02_image091
、
Figure 02_image093
或
Figure 02_image095
； R 5至R 14各自為氫、氟、氯 、R 15、‒CN、‒OR 16、‒SR 17、‒C(=O)OR 18、芳基、雜芳基或‒Si(R 19) 3； R 15至R 19各自為C 4~C 30直鏈烷基、C 4~C 30支鏈烷基、C 4~C 30環烷基、C 4~C 30烯基或C 4~C 30炔基，且R 15至R 19各自為未經取代或經至少一個R 20取代； R 20為鹵素、‒CN或-SiR 21R 22R 23； R 21至R 23各自為C 1~C 30烷基； Ar為亞芳基或亞雜芳基； X與Z各自為‒CH 2‒或‒O‒；及 Y為C 1~C 20直鏈亞烷基、C 3~C 20支鏈亞烷基或C 3~C 20亞環烷基。 Therefore, the second non-fullerene electron acceptor material of the present invention is a polymer acceptor material, and contains a repeating unit represented by the following formula (II): [Formula II]
Figure 02_image043
Wherein, R 1 is C 1 ~C 30 alkyl; D is
Figure 02_image045
,
Figure 02_image047
,
Figure 02_image049
,
Figure 02_image051
,
Figure 02_image053
,
Figure 02_image055
,
Figure 02_image057
,
Figure 02_image059
,
Figure 02_image061
,
Figure 02_image063
,
Figure 02_image065
,
Figure 02_image067
,
Figure 02_image069
or
Figure 02_image071
； R 2 is hydrogen, C 1 to C 30 alkyl, C 1 to C 30 alkoxy, C 1 to C 30 alkyl aryl, or C 1 to C 30 alkyl heteroaryl; E is
Figure 02_image073
,
Figure 02_image075
,
Figure 02_image077
,
Figure 02_image079
,
Figure 02_image081
or
Figure 02_image083
； R 3 is hydrogen, halogen, C 1 ~C 30 alkyl or C 1 ~C 30 alkoxy; L is
Figure 02_image085
,
Figure 02_image087
,
Figure 02_image089
,
Figure 02_image091
,
Figure 02_image093
or
Figure 02_image095
； R 5 to R 14 are each hydrogen, fluorine, chlorine, R 15 , ‒CN, ‒OR 16 , ‒SR 17 , ‒C(=O)OR 18 , aryl, heteroaryl, or ‒Si(R 19 ) 3 ; R 15 to R 19 are each C 4 to C 30 linear alkyl, C 4 to C 30 branched alkyl, C 4 to C 30 cycloalkyl, C 4 to C 30 alkenyl or C 4 to C 30 Alkynyl, and R 15 to R 19 are each unsubstituted or substituted with at least one R 20 ; R 20 is halogen, ‒CN or -SiR 21 R 22 R 23 ; R 21 to R 23 are each C 1 to C 30 Alkyl; Ar is arylene or heteroarylene; X and Z are each ‒CH 2 ‒ or ‒O‒; and Y is C 1 ~C 20 linear alkylene, C 3 ~C 20 branched alkylene Alkyl group or C 3 ~C 20 cycloalkylene group.

因此，本發明之第三目的，即在提供一種有機光伏電池。Therefore, the third object of the present invention is to provide an organic photovoltaic cell.

於是，本發明有機光伏電池包含一主動層，該主動層包括前述兩種非富勒烯電子受體材料中的其中一種非富勒烯電子受體材料。Therefore, the organic photovoltaic cell of the present invention includes an active layer that includes one of the aforementioned two non-fullerene electron acceptor materials.

本發明之功效在於：由於本發明非富勒烯電子受體材料包含苯并硒二唑中心基團與推電子基團，且利用氮原子連接成多稠環結構，同時以強拉電子基團連接兩端，因而相較於現有的非富勒烯電子受體材料，本發明的非富勒烯電子受體材料之吸收光譜範圍能有效延長至近紅外光區域，進而能有效捕獲更多近紅外光區的太陽光光子。The effect of the present invention is: because the non-fullerene electron acceptor material of the present invention contains a benzoselenodiazole central group and an electron donating group, and the nitrogen atom is connected to form a multi-fused ring structure, and at the same time, it uses a strong electron withdrawing group The two ends are connected. Therefore, compared with the existing non-fullerene electron acceptor material, the absorption spectrum of the non-fullerene electron acceptor material of the present invention can be effectively extended to the near-infrared light region, thereby effectively capturing more near-infrared light. Sunlight photons in the light zone.

以下將就本發明內容進行詳細說明：The content of the present invention will be described in detail below:

需先說明的是，本發明中所述的「烷基芳基」及「烷基雜芳基」所指分別為「經烷基取代的芳基」及「經烷基取代的雜芳基」，且「烷基芳基」或「烷基雜芳基」前的碳數所指為烷基的碳數，例如C 1~C 30烷基芳基所指為經C 1~C 30烷基取代的芳基。 It should be noted that the "alkylaryl" and "alkylheteroaryl" in the present invention refer to "alkyl substituted aryl" and "alkyl substituted heteroaryl" respectively , And the carbon number before "alkylaryl" or "alkylheteroaryl" refers to the carbon number of the alkyl group. For example, a C 1 ~C 30 alkyl aryl group refers to a C 1 ~C 30 alkyl group Substituted aryl.

[第一種非富勒烯電子受體材料][The first non-fullerene electron acceptor material]

本發明第一種非富勒烯電子受體材料，如下式(I)所示： [式I]

Figure 02_image001
其中，R 1與A的定義如前所述。 The first non-fullerene electron acceptor material of the present invention is represented by the following formula (I): [Formula I]
Figure 02_image001
Wherein, the definitions of R 1 and A are as described above.

先說明的是，本發明式(I)中的A，其是以相鄰的兩個星號(*)位置與苯并硒二唑中心基團連接，舉例說明，是以下式(a)箭頭所指的兩個位置與苯并硒二唑中心基團連接，而得到下式(b)的結構。 [式a]

Figure 02_image097
[式b]
Figure 02_image099
Firstly, the A in formula (I) of the present invention is connected to the central group of benzoselenodiazole by two adjacent asterisk (*) positions. For example, it is indicated by the arrow of the following formula (a) The two positions referred to are connected with the central group of benzoselenodiazole to obtain the structure of the following formula (b). [Formula a]
Figure 02_image097
[Formula b]
Figure 02_image099

較佳地，A為

Figure 02_image007
。更佳地，R 2為C 6~C 16烷基。又更佳地，R 2為C 9~C 13烷基。 Preferably, A is
Figure 02_image007
. More preferably, R 2 is a C 6 to C 16 alkyl group. Still more preferably, R 2 is a C 9 to C 13 alkyl group.

較佳地，B為

Figure 02_image033
。更佳地，R 3為氫或鹵素。 Preferably, B is
Figure 02_image033
. More preferably, R 3 is hydrogen or halogen.

較佳地，R 1為C 3~C 13烷基。更佳地，R 1為C 3~C 13支鏈烷基。更佳地，R 1為C 6~C 10烷基。又更佳地，R 1為C 6~C 10支鏈烷基。 Preferably, R 1 is a C 3 to C 13 alkyl group. More preferably, R 1 is a C 3 to C 13 branched alkyl group. More preferably, R 1 is a C 6 to C 10 alkyl group. Still more preferably, R 1 is a C 6 to C 10 branched alkyl group.

[第二種非富勒烯電子受體材料][The second non-fullerene electron acceptor material]

本發明第二種非富勒烯電子受體材料，包含下式(II)所示的重複單元： [式II]

Figure 02_image043
其中，R 1、D、E與L的定義如前所述。 The second non-fullerene electron acceptor material of the present invention comprises a repeating unit represented by the following formula (II): [Formula II]
Figure 02_image043
Wherein, the definitions of R 1 , D, E and L are as described above.

需先說明的是，本發明式(II)中的D，其是以相鄰的兩個星號(*)位置與苯并硒二唑中心基團連接，舉例說明，是以下式(c)箭頭所指的兩個位置與苯并硒二唑中心基團連接，而得到下式(d)的結構。 [式c]

Figure 02_image101
[式d]
Figure 02_image103
It should be noted that D in the formula (II) of the present invention is connected to the central group of the benzoselenodiazole by two adjacent asterisks (*). For example, it is the arrow of the following formula (c) The two positions indicated are connected with the central group of benzoselenodiazole to obtain the structure of the following formula (d). [Formula c]
Figure 02_image101
[Formula d]
Figure 02_image103

較佳地，D為

Figure 02_image105
或
Figure 02_image045
。更佳地，R 2為氫或C 6~C 16烷基。又更佳地，R 2為氫或C 9~C 13烷基。 Preferably, D is
Figure 02_image105
or
Figure 02_image045
. More preferably, R 2 is hydrogen or C 6 to C 16 alkyl. Still more preferably, R 2 is hydrogen or C 9 to C 13 alkyl.

較佳地，E為

Figure 02_image075
、
Figure 02_image077
或
Figure 02_image083
。更佳地，R 3為氫或鹵素。 Preferably, E is
Figure 02_image075
,
Figure 02_image077
or
Figure 02_image083
. More preferably, R 3 is hydrogen or halogen.

較佳地，E是以遠離苯基或噻吩基的星號(*)位置與D連接，舉例說明，是以下式(e)箭頭所指位置與D連接，而得到下式(f)的結構。 [式e]

Figure 02_image109
[式f]
Figure 02_image111
Preferably, E is connected to D at a position away from the asterisk (*) of the phenyl or thienyl group. For example, the position indicated by the arrow of the following formula (e) is connected to D to obtain the structure of the following formula (f). [Formula e]
Figure 02_image109
[Formula f]
Figure 02_image111

較佳的，L為

Figure 02_image087
、
Figure 02_image089
或
Figure 02_image091
。更佳地，R 7至R 14各自為氫。 Preferably, L is
Figure 02_image087
,
Figure 02_image089
or
Figure 02_image091
. More preferably, R 7 to R 14 are each hydrogen.

較佳地，R 1為C 3~C 13烷基。更佳地，R 1為C 3~C 13支鏈烷基。更佳地，R 1為C 6~C 10烷基。又更佳地，R 1為C 6~C 10支鏈烷基。 Preferably, R 1 is a C 3 to C 13 alkyl group. More preferably, R 1 is a C 3 to C 13 branched alkyl group. More preferably, R 1 is a C 6 to C 10 alkyl group. Still more preferably, R 1 is a C 6 to C 10 branched alkyl group.

>實施例1與2>>Examples 1 and 2>

製備非富勒烯電子受體材料Preparation of non-fullerene electron acceptor materials

實施例1與2的非富勒烯電子受體材料之製備流程如下列反應式I(實施例1)與反應式II(實施例2)所示。 [反應式I]

Figure 02_image114
[反應式II]
Figure 02_image116
化合物1
Figure 02_image118
化合物1的製備方法： 將4,7-二溴-苯并噻二唑(20 g, 68.034 mmol)溶於乙醇(EtOH)( 200 mL)，分批次加入硼氫化鈉(NaBH 4)(10.3 g, 272.14 mmol)並加熱迴流(reflux)4小時。待反應結束後冷卻，以二氯甲烷、水、鹼水萃取。有機層以無水硫酸鎂乾燥、過濾，並以迴旋濃縮機濃縮抽乾，即可得到微黃色固體之化合物1(12.5 g, 產率: 69%)。 化合物2
Figure 02_image120
化合物2的製備方法： 將化合物1(2 g, 7.52 mmol)溶於乙醇(20 mL)裝入100 mL三頸瓶，接著將二氧化硒(SeO 2)(1g, 9.02 mmol)溶於水(10 mL)後慢慢滴入反應瓶中，並加熱迴流16小時，待反應結束後冷卻，以甲醇為沖堤液過濾得黃色固體之化合物2(2 g, 產率: 78%)。 化合物3
Figure 02_image122
化合物3的製備方法： 在冰浴下，將濃硫酸(conc. H 2SO 4)(112 mL)和發煙硝酸(fuming HNO 3)(112 mL)混合裝入500 mL三頸瓶中，再慢慢倒入化合物2(14g, 41.07 mmol)並於50℃下加熱18小時，待反應結束後冷卻，倒入冰水產生固體，並將固體過濾後，得淡黃色固體之化合物3(5.3 g, 產率: 30%)。 化合物5
Figure 02_image124
化合物5的製備方法： 在100 mL圓底燒瓶中，將4,7-二溴-5,6-二硝基苯並硒二唑(化合物3)(2.5 g, 5.8 mmol)、2-三丁基錫烷基噻吩(化合物 4)(6.1 g, 12.2 mmol) 、三(2-呋喃基)膦[P(o-tolyl) 3](0.18 g, 0.58 mmol)及三(二亞苄基丙酮)二鈀[Pd 2(dba) 3](0.16 g, 0.17 mmol)溶於50 mL甲苯中，在氮氣保護下加熱迴流2小時。冷卻後以二氯甲烷萃取，以矽膠管柱層 (二氯甲烷：正庚烷=1：2為沖提液)純化，得到紅色固體化合物5(4.2 g，產率：85%) 。 化合物6
Figure 02_image126
化合物6的製備方法： 化合物 5(1 g, 1.17 mmol)、三苯基膦(PPh 3)(2.45 g, 9.32 mmol)加入至100mL圓底瓶中，隨後加入20 mL的鄰二氯苯(o-DCB)，在氮氣保護下加熱迴流14小時。冷卻後加入庚烷產生固體，並將固體過濾，真空乾燥後得到橘紅色固體之化合物6(1.9 g, 產率:49%)。 化合物7
Figure 02_image128
化合物7的製備方法： 在100 mL圓底燒瓶中，化合物6(2 g, 3.15 mmol)、1-碘-2-乙基己烷(4.67 g, 15.75 mmol)溶於30 mL二甲基甲醯胺(DMF)中，緩慢加入碳酸鉀(K 2CO 3)(3.5 g, 25.2 mmol)，在氮氣保護下90℃加熱迴流2小時。反應結束後以乙酸乙酯萃取，有機層以無水硫酸鎂乾燥、過濾，並以迴旋濃縮機濃縮抽乾，最後以矽膠管柱層析(二氯甲烷：正庚烷 =1：1為沖提液)進行純化，真空乾燥後得到土黃色固體化合物7(3 g, 產率: 98%)。 化合物8
Figure 02_image130
化合物8的製備方法： 於100 mL的圓底瓶當中，加入化合物 7(3 g, 3.09 mmol)及無水二甲基甲醯胺(DMF)(14.3 mL, 185.22 mmol)溶於45 mL 1,2-二氯乙烷(DCE)中。在冰浴下緩慢加入三氯氧磷(POCl 3)(5.76 mL, 61.75 mmol)，隨後緩慢升溫至迴流，攪拌16小時。反應結束後以二氯甲烷加入進行萃取，有機層以無水硫酸鎂乾燥、過濾，並以迴旋濃縮機濃縮抽乾，最後以矽膠管柱層析(二氯甲烷：正庚烷 =3：2)進行純化，真空乾燥後得到橘紅色固體化合物8(2.5 g, 產率: 78%)。 實施例1
Figure 02_image132
實施例1的製備方法： 將化合物8(1 g, 0.09 mmol)及3-(二氰基亞甲基)靛酮(化合物9)(0.73 g, 0.37 mmol) 加入250 mL圓底瓶中，隨後加入100 mL 氯仿(CHCl 3)溶解，緩慢滴入吡啶(pyridine)2 mL，在氮氣保護下加熱迴流5小時，待反應結束後冷卻，以迴旋濃縮機濃縮抽乾。接著以甲醇析出固體後，再以矽膠管柱層析(石油醚/氯仿)進行純化，經真空乾燥後得到深藍色固體即為實施例1(1.1 g, 產率: 82%)。 實施例2
Figure 02_image134
實施例2的製備方法： 化合物8(0.3 g, 0.28 mmol)及2F-IC(化合物10)(0.32 g, 1.40 mmol)加入100 mL圓底瓶中，隨後加入30 mL氯仿溶解，緩慢滴入吡啶 1 mL，在氮氣保護下加熱迴流2小時，待反應結束後冷卻，以迴旋濃縮機濃縮抽乾。接著以甲醇析出固體後，再以矽膠管柱層析(石油醚/氯仿)進行純化，真空乾燥後得到深藍色固體即為實施例2(0.3 g, 產率: 73%)。 The preparation process of the non-fullerene electron acceptor materials of Examples 1 and 2 is shown in the following reaction formula I (Example 1) and reaction formula II (Example 2). [Reaction formula I]
Figure 02_image114
[Reaction formula II]
Figure 02_image116
Compound 1
Figure 02_image118
The preparation method of compound 1: 4,7-dibromo-benzothiadiazole (20 g, 68.034 mmol) was dissolved in ethanol (EtOH) (200 mL), sodium borohydride (NaBH 4 ) (10.3 g, 272.14 mmol) and reflux (reflux) for 4 hours. After the reaction is over, it is cooled and extracted with dichloromethane, water, and alkaline water. The organic layer was dried with anhydrous magnesium sulfate, filtered, and concentrated and drained with a cyclonic concentrator to obtain compound 1 (12.5 g, yield: 69%) as a yellowish solid. Compound 2
Figure 02_image120
Preparation method of compound 2: Dissolve compound 1 (2 g, 7.52 mmol) in ethanol (20 mL) into a 100 mL three-necked flask, and then dissolve selenium dioxide (SeO 2 ) (1 g, 9.02 mmol) in water ( 10 mL) was slowly dropped into the reaction flask and heated to reflux for 16 hours. After the reaction was completed, it was cooled and filtered with methanol as the flushing liquid to obtain compound 2 (2 g, yield: 78%) as a yellow solid. Compound 3
Figure 02_image122
The preparation method of compound 3: Under ice bath, mix concentrated sulfuric acid (conc. H 2 SO 4 ) (112 mL) and fuming HNO 3 (112 mL) into a 500 mL three-necked flask, and then Slowly pour compound 2 (14g, 41.07 mmol) and heat at 50°C for 18 hours. After the reaction is over, cool down, pour into ice water to produce a solid, and filter the solid to obtain compound 3 (5.3 g) as a pale yellow solid , Yield: 30%). Compound 5
Figure 02_image124
The preparation method of compound 5: In a 100 mL round-bottom flask, mix 4,7-dibromo-5,6-dinitrobenzoselenodiazole (compound 3) (2.5 g, 5.8 mmol), 2-tributyltin Alkylthiophene (compound 4) (6.1 g, 12.2 mmol), tris(2-furyl)phosphine [P(o-tolyl) 3 ] (0.18 g, 0.58 mmol) and tris(dibenzylideneacetone) dipalladium [Pd 2 (dba) 3 ] (0.16 g, 0.17 mmol) was dissolved in 50 mL of toluene and heated to reflux for 2 hours under nitrogen protection. After cooling, it was extracted with dichloromethane, and purified with a silica gel column (dichloromethane: n-heptane=1: 2 as the eluent) to obtain a red solid compound 5 (4.2 g, yield: 85%). Compound 6
Figure 02_image126
The preparation method of compound 6: Compound 5 (1 g, 1.17 mmol), triphenylphosphine (PPh 3 ) (2.45 g, 9.32 mmol) were added to a 100 mL round bottom flask, and then 20 mL of o-dichlorobenzene (o -DCB), heated to reflux for 14 hours under the protection of nitrogen. After cooling, heptane was added to produce a solid, and the solid was filtered and dried under vacuum to obtain compound 6 (1.9 g, yield: 49%) as an orange solid. Compound 7
Figure 02_image128
Preparation method of compound 7: In a 100 mL round-bottom flask, compound 6 (2 g, 3.15 mmol) and 1-iodo-2-ethylhexane (4.67 g, 15.75 mmol) were dissolved in 30 mL dimethylformamide To the amine (DMF), slowly add potassium carbonate (K 2 CO 3 ) (3.5 g, 25.2 mmol), and heat to reflux at 90° C. for 2 hours under the protection of nitrogen. After the reaction, it was extracted with ethyl acetate, the organic layer was dried with anhydrous magnesium sulfate, filtered, and concentrated with a cyclonic concentrator to drain, and finally purified by silica gel column chromatography (dichloromethane: n-heptane=1:1) Liquid) for purification and vacuum drying to obtain an ocher solid compound 7 (3 g, yield: 98%). Compound 8
Figure 02_image130
Preparation method of compound 8: In a 100 mL round bottom flask, add compound 7 (3 g, 3.09 mmol) and anhydrous dimethylformamide (DMF) (14.3 mL, 185.22 mmol) in 45 mL 1,2 -Dichloroethane (DCE). Phosphorus oxychloride (POCl 3 ) (5.76 mL, 61.75 mmol) was slowly added in an ice bath, and then slowly heated to reflux, and stirred for 16 hours. After the reaction is over, dichloromethane is added for extraction, the organic layer is dried with anhydrous magnesium sulfate, filtered, and concentrated with a cyclonic concentrator to drain, and finally chromatographed with silica gel column (dichloromethane: n-heptane=3:2) After purification and vacuum drying, an orange-red solid compound 8 (2.5 g, yield: 78%) was obtained. Example 1
Figure 02_image132
The preparation method of Example 1: Add compound 8 (1 g, 0.09 mmol) and 3-(dicyanomethylene)indigo (compound 9) (0.73 g, 0.37 mmol) into a 250 mL round-bottomed flask, and then Add 100 mL of chloroform (CHCl 3 ) to dissolve, slowly drop in 2 mL of pyridine, heat to reflux for 5 hours under the protection of nitrogen, cool after the reaction is completed, and concentrate and drain with a cyclone concentrator. Then, the solid was precipitated with methanol, and then purified by silica gel column chromatography (petroleum ether/chloroform). After vacuum drying, a dark blue solid was obtained as Example 1 (1.1 g, yield: 82%). Example 2
Figure 02_image134
The preparation method of Example 2: Compound 8 (0.3 g, 0.28 mmol) and 2F-IC (Compound 10) (0.32 g, 1.40 mmol) were added to a 100 mL round bottom flask, then 30 mL of chloroform was added to dissolve, and pyridine was slowly dropped into it 1 mL, heated to reflux for 2 hours under the protection of nitrogen, cooled after completion of the reaction, concentrated and drained with a cyclone concentrator. After the solid was precipitated with methanol, it was purified by silica gel column chromatography (petroleum ether/chloroform), and the dark blue solid was obtained after vacuum drying, which was Example 2 (0.3 g, yield: 73%).

>實施例3至6>>Examples 3 to 6>

製備高分子非富勒烯電子受體材料Preparation of polymer non-fullerene electron acceptor materials

含有實施例3至6之重複單元的高分子非富勒烯電子受體材料結構分別如下所示。 [實施例3]

Figure 02_image136
[實施例4]
Figure 02_image138
[實施例5]
Figure 02_image140
[實施例6]
Figure 02_image142
The structures of the polymer non-fullerene electron acceptor materials containing the repeating units of Examples 3 to 6 are as follows, respectively. [Example 3]
Figure 02_image136
[Example 4]
Figure 02_image138
[Example 5]
Figure 02_image140
[Example 6]
Figure 02_image142

含有實施例3至5之重複單元的高分子非富勒烯電子受體材料之製備流程如下列反應式III所示。 [反應式III]

Figure 02_image144
其中， ‒E‒為
Figure 02_image146
(實施例3與4)或
Figure 02_image148
(實施例5)；及 ‒L‒為
Figure 02_image150
(實施例3與5)或
Figure 02_image152
(實施例4)。 The preparation process of the polymer non-fullerene electron acceptor material containing the repeating units of Examples 3 to 5 is shown in the following reaction formula III. [Reaction formula III]
Figure 02_image144
Where ‒E‒ is
Figure 02_image146
(Examples 3 and 4) or
Figure 02_image148
(Example 5); and ‒L‒ is
Figure 02_image150
(Examples 3 and 5) or
Figure 02_image152
(Example 4).

含有實施例6之重複單元的高分子非富勒烯電子受體材料之製備流程如下列反應式IV所示。 [反應式IV]

Figure 02_image154
其中， ‒E‒為
Figure 02_image146
；及 ‒L‒為
Figure 02_image156
。 實施例3至6的製備方法： 需先說明的是，化合物9的製備方法類似於前述化合物8的製備方法，其主要差別在於，化合物9在製備過程中是利用
Figure 02_image158
與化合物3進行反應。而實施例3至6的製備方法為將化合物8(化合物9)及帶有經溴取代的拉電子基團(E-Br)於氯仿與吡啶的存在下進行縮合反應，以得到化合物11(化合物12)。接著，化合物11(化合物12)再與芳香雙錫化合物(Me 3Sn‒L‒SnMe 3)溶於氯苯(chlorobenzene)，並於三(2-呋喃基)膦及三(二亞苄基丙酮)二鈀的存在下迴流，並進行共軛聚合反應，即可以分別得到含有實施例3至6所示之重複單元的高分子非富勒烯電子受體材料。 The preparation process of the polymer non-fullerene electron acceptor material containing the repeating unit of Example 6 is shown in the following reaction formula IV. [Reaction formula IV]
Figure 02_image154
Where ‒E‒ is
Figure 02_image146
; And ‒L‒ is
Figure 02_image156
. Preparation methods of Examples 3 to 6: It should be noted that the preparation method of compound 9 is similar to the preparation method of compound 8 mentioned above, the main difference is that compound 9 is used in the preparation process
Figure 02_image158
React with compound 3. The preparation methods of Examples 3 to 6 are compound 8 (compound 9) and an electron withdrawing group (E-Br) substituted by bromine in the presence of chloroform and pyridine for condensation reaction to obtain compound 11 (compound 12). Next, compound 11 (compound 12) is dissolved in chlorobenzene (chlorobenzene) with the aromatic bistin compound (Me 3 Sn‒L‒SnMe 3 ), and then dissolved in tris(2-furyl)phosphine and tris(dibenzylideneacetone). ) Reflux in the presence of dipalladium and carry out a conjugate polymerization reaction to obtain polymer non-fullerene electron acceptor materials containing the repeating units shown in Examples 3 to 6, respectively.

>光性質分析>>Optical Properties Analysis>

測試方法：Test Methods:

以紫外光/可見光光譜儀(UV/Vis Spectrophotometer)量測實施例1與2，以及Y5與Y6(結構如下列所示)之非富勒烯電子受體材料的UV/Vis吸收光譜，所得結果如圖1所示。

Figure 02_image160
The UV/Vis spectrophotometer was used to measure the UV/Vis absorption spectra of the non-fullerene electron acceptor materials of Examples 1 and 2, and Y5 and Y6 (structures are shown below). The results are as follows As shown in Figure 1.
Figure 02_image160

結果與討論：Results and discussion:

檢視實施例1和實施例2之吸收光譜(圖1)，其兩者溶液態吸收波長涵蓋 600~900 nm，擴展到了近紅外光區，而最大吸收波長分別為769 nm與784 nm，顯示實施例1與2之非富勒烯電子受體材料可充分吸收紅光甚至到近紅外光區。因此，相較於現有之非富勒烯電子受體材料(Y5和Y6)，本發明之非富勒烯電子受體材料(實施例1與2)的吸收分別紅移了50 nm與52 nm，說明相較於現有之非富勒烯電子受體材料，本發明之非富勒烯電子受體材料的吸收光譜範圍能有效延長至近紅外光區域，進而能有效捕獲更多近紅外光區的太陽光光子。Check the absorption spectra of Example 1 and Example 2 (Figure 1). The solution absorption wavelengths of both of them cover 600~900 nm and extend to the near-infrared region. The maximum absorption wavelengths are 769 nm and 784 nm, respectively. The non-fullerene electron acceptor materials of Examples 1 and 2 can fully absorb red light even to the near-infrared light region. Therefore, compared with the existing non-fullerene electron acceptor materials (Y5 and Y6), the absorption of the non-fullerene electron acceptor material of the present invention (Examples 1 and 2) is red-shifted by 50 nm and 52 nm, respectively , Which shows that compared with the existing non-fullerene electron acceptor materials, the absorption spectrum range of the non-fullerene electron acceptor material of the present invention can be effectively extended to the near-infrared light region, thereby effectively capturing more near-infrared light region Sunlight photon.

>應用例>>Application Examples>

有機光伏電池Organic photovoltaic cells

參閱圖2，為一應用例的有機光伏電池。該有機光伏電池包含一主動層92、一電子傳輸層91、一電洞傳輸層93、一負極80、一正極100及一基板70。Refer to Figure 2 for an organic photovoltaic cell of an application example. The organic photovoltaic cell includes an active layer 92, an electron transport layer 91, a hole transport layer 93, a negative electrode 80, a positive electrode 100, and a substrate 70.

該電子傳輸層91與該電洞傳輸層93分別位於該主動層92的兩相反側。該負極80位於該電子傳輸層91相反於該主動層92的一側，該正極100位於該電洞傳輸層93相反於該主動層92的一側。該基板70位於該負極80相反於該電子傳輸層91的一側。The electron transport layer 91 and the hole transport layer 93 are respectively located on two opposite sides of the active layer 92. The negative electrode 80 is located on the side of the electron transport layer 91 opposite to the active layer 92, and the positive electrode 100 is located on the side of the hole transport layer 93 opposite to the active layer 92. The substrate 70 is located on the side of the negative electrode 80 opposite to the electron transport layer 91.

在本具體應用例中，該主動層92包括實施例1至6其中一種的非富勒烯電子受體材料(作為電子受體材料)及共軛聚合物(作為電子給體材料，結構如下所示)，且該非富勒烯電子受體材料與該共軛聚合物的重量比值為1。該電子傳輸層91的材料為氧化鋅(ZnO)。該電洞傳輸層93的材料為三氧化鉬(MoO­ 3)。該負極80的材料為氧化銦錫(ITO)。該正極100的材料為銀。該基板70的材料為玻璃。 [共軛聚合物]

Figure 02_image162
In this specific application example, the active layer 92 includes the non-fullerene electron acceptor material (as an electron acceptor material) and a conjugated polymer (as an electron donor material) of one of the embodiments 1 to 6, and the structure is as follows ), and the weight ratio of the non-fullerene electron acceptor material to the conjugated polymer is 1. The material of the electron transport layer 91 is zinc oxide (ZnO). The material of the hole transport layer 93 is molybdenum trioxide (MoO 3 ). The material of the negative electrode 80 is indium tin oxide (ITO). The material of the positive electrode 100 is silver. The material of the substrate 70 is glass. [Conjugated Polymer]
Figure 02_image162

以下同時參閱圖2，說明本應用例之有機光伏電池的製備方法： 步驟(1)-製備玻璃基板70與正極80：將已圖樣化的氧化銦錫(ITO)玻璃基板(12 Ω/□)於超音波震盪槽中依序使用清潔劑、去離子水、丙酮及異丙醇分別清洗10分鐘。ITO玻璃基板經過超音波震盪清洗後，於紫外光臭氧(UV-ozone)清潔機中進行表面處理30分鐘。其中，玻璃基板即為該基板70，ITO即為該負極80。 步驟(2)-製備電子傳輸層91：將二乙基鋅(ZnEt 2)溶液旋轉塗佈於經步驟(1)處理後的ITO玻璃基板上，並於手套箱中以120℃的溫度烘烤20分鐘，以於該負極80上形成一ZnO層(即該電子傳輸層91)。 步驟(3)-製備主動層92：將實施例1至6其中一種的非富勒烯電子受體材料與共軛聚合物混和(重量比1：1)，並以氯苯為溶劑調製成主動層溶液。將該主動層溶液旋轉塗佈於該電子傳輸層91上，並於氮氣環境及100℃的溫度下烘烤10分鐘，以形成該主動層92。 步驟(4)-製備電洞傳輸層93：將由步驟(3)所得的半成品送入一真空腔體內。接著，加熱沉積約4 nm的三氧化鉬(MoO 3)於該主動層92上，以形成該電洞傳輸層93。 The following also refers to Figure 2 to illustrate the preparation method of the organic photovoltaic cell of this application example: Step (1)-Preparation of glass substrate 70 and positive electrode 80: Patterned indium tin oxide (ITO) glass substrate (12 Ω/□) Use detergent, deionized water, acetone and isopropanol to wash in the ultrasonic tank for 10 minutes. After the ITO glass substrate was cleaned by ultrasonic vibration, the surface treatment was performed in a UV-ozone cleaning machine for 30 minutes. Among them, the glass substrate is the substrate 70, and ITO is the negative electrode 80. Step (2)-Preparation of electron transport layer 91: spin-coated diethyl zinc (ZnEt 2 ) solution on the ITO glass substrate treated in step (1), and baked in a glove box at a temperature of 120°C For 20 minutes, a ZnO layer (ie, the electron transport layer 91) is formed on the negative electrode 80. Step (3)-Preparation of active layer 92: The non-fullerene electron acceptor material of one of Examples 1 to 6 is mixed with conjugated polymer (weight ratio 1:1), and chlorobenzene is used as a solvent to prepare the active layer. Layer solution. The active layer solution was spin-coated on the electron transport layer 91 and baked under a nitrogen atmosphere and a temperature of 100° C. for 10 minutes to form the active layer 92. Step (4)-Preparation of hole transport layer 93: The semi-finished product obtained in step (3) is sent into a vacuum chamber. Then, molybdenum trioxide (MoO 3 ) of about 4 nm is heated and deposited on the active layer 92 to form the hole transport layer 93.

步驟(5)-製備正負極100：於該電動傳輸層93上加熱沉積約100 nm的銀，以形成該正極100。Step (5)-Preparation of the positive and negative electrodes 100: heating and depositing about 100 nm of silver on the electrokinetic transport layer 93 to form the positive electrode 100.

綜上所述，由於本發明非富勒烯電子受體材料包含苯并硒二唑中心基團與推電子基團，且利用氮原子連接成多稠環結構，同時以強拉電子基團連接兩端，因而相較於現有的非富勒烯電子受體材料，本發明的非富勒烯電子受體材料吸收光譜範圍能有效延長至近紅外光區域，進而能有效捕獲更多近紅外光區的太陽光光子，故確實能達成本發明之目的。To sum up, because the non-fullerene electron acceptor material of the present invention contains a benzoselenodiazole central group and an electron donating group, and the nitrogen atom is connected to form a multi-fused ring structure, and at the same time, it is connected with a strong electron withdrawing group At both ends, compared with the existing non-fullerene electron acceptor material, the absorption spectrum range of the non-fullerene electron acceptor material of the present invention can be effectively extended to the near-infrared light region, thereby effectively capturing more near-infrared light regions The sunlight photon, so it can indeed achieve the purpose of the invention.

惟以上所述者，僅為本發明之實施例而已，當不能以此限定本發明實施之範圍，凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。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:基板 80:負極 91:電子傳輸層 92:主動層 93:電洞傳輸層 100:正極70: substrate 80: negative electrode 91: electron transport layer 92: active layer 93: hole transport layer 100: positive

本發明之其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中： 圖1是一實施例1與2及Y5與Y6之非富勒烯電子受體材料的UV/Vis吸收光譜圖；及 圖2是一示意圖，說明應用例的有機光伏電池。Other features and effects of the present invention will be clearly presented in the embodiments with reference to the drawings, in which: Figure 1 is a UV/Vis absorption spectra of the non-fullerene electron acceptor materials of Examples 1 and 2 and Y5 and Y6; and Fig. 2 is a schematic diagram illustrating an organic photovoltaic cell of an application example.

Figure 01_image002
Figure 01_image002

Claims (10)

一種非富勒烯電子受體材料，如下式(I)所示： [式I]
Figure 03_image001
其中， R 1為C 1~C 30­烷基； A為
Figure 03_image003
、
Figure 03_image005
、
Figure 03_image007
、
Figure 03_image009
、
Figure 03_image011
、
Figure 03_image013
、
Figure 03_image015
、
Figure 03_image017
、
Figure 03_image019
、
Figure 03_image021
、
Figure 03_image023
、
Figure 03_image025
、
Figure 03_image027
或
Figure 03_image029
；
R 2為氫、C 1~C 30烷基、C 1~C 30烷氧基、C 1~C 30烷基芳基或C 1~C 30烷基雜芳基； B為
Figure 03_image031
、
Figure 03_image033
、
Figure 03_image035
、
Figure 03_image037
、
Figure 03_image039
或
Figure 03_image041
；
R 3為氫、鹵素、C 1~C 30烷基或C 1~C 30烷氧基；及 R 4為氫或C 1~C 30烷基。 A non-fullerene electron acceptor material, as shown in the following formula (I): [Formula I]
Figure 03_image001
Wherein, R 1 is a C 1 ~C 30 alkyl group; A is
Figure 03_image003
,
Figure 03_image005
,
Figure 03_image007
,
Figure 03_image009
,
Figure 03_image011
,
Figure 03_image013
,
Figure 03_image015
,
Figure 03_image017
,
Figure 03_image019
,
Figure 03_image021
,
Figure 03_image023
,
Figure 03_image025
,
Figure 03_image027
or
Figure 03_image029
；
R 2 is hydrogen, C 1 to C 30 alkyl, C 1 to C 30 alkoxy, C 1 to C 30 alkyl aryl, or C 1 to C 30 alkyl heteroaryl; B is
Figure 03_image031
,
Figure 03_image033
,
Figure 03_image035
,
Figure 03_image037
,
Figure 03_image039
or
Figure 03_image041
；
R 3 is hydrogen, halogen, C 1 to C 30 alkyl or C 1 to C 30 alkoxy; and R 4 is hydrogen or C 1 to C 30 alkyl. 如請求項1所述的非富勒烯電子受體材料，其中，A為
Figure 03_image007
。 The non-fullerene electron acceptor material according to claim 1, wherein A is
Figure 03_image007
. 如請求項2所述的非富勒烯電子受體材料，其中，R 2為C 6~C 16烷基。 The non-fullerene electron acceptor material according to claim 2, wherein R 2 is a C 6 to C 16 alkyl group. 如請求項1所述的非富勒烯電子受體材料，其中，B為
Figure 03_image033
。 The non-fullerene electron acceptor material according to claim 1, wherein B is
Figure 03_image033
. 如請求項4所述的非富勒烯電子受體材料，其中，R 3為氫或鹵素。 The non-fullerene electron acceptor material according to claim 4, wherein R 3 is hydrogen or halogen. 如請求項1所述的非富勒烯電子受體材料，其中，R 1為C 3~C 13烷基。 The non-fullerene electron acceptor material according to claim 1, wherein R 1 is a C 3 to C 13 alkyl group. 如請求項6所述的非富勒烯電子受體材料，其中，R 1為C 3~C 13支鏈烷基。 The non-fullerene electron acceptor material according to claim 6, wherein R 1 is a C 3 to C 13 branched alkyl group. 一種非富勒烯電子受體材料，包含下式(II)所示的重複單元： [式II]
Figure 03_image043
其中， R 1為C 1~C 30­烷基； D為
Figure 03_image045
、
Figure 03_image047
、
Figure 03_image049
、
Figure 03_image051
、
Figure 03_image053
、
Figure 03_image055
、
Figure 03_image057
、
Figure 03_image059
、
Figure 03_image061
、
Figure 03_image063
、
Figure 03_image065
、
Figure 03_image067
、
Figure 03_image069
或
Figure 03_image071
；
R 2為氫、C 1~C 30烷基、C 1~C 30烷氧基、C 1~C 30烷基芳基 或C 1~C 30烷基雜芳基； E為
Figure 03_image073
、
Figure 03_image075
、
Figure 03_image077
、
Figure 03_image079
、
Figure 03_image081
或
Figure 03_image083
；
R 3為氫、鹵素、C 1~C 30烷基或C 1~C 30烷氧基； L為
Figure 03_image206
、
Figure 03_image087
、
Figure 03_image089
、
Figure 03_image091
、
Figure 03_image093
或
Figure 03_image095
；
R 5至R 14各自為氫、氟、氯 、R 15、‒CN、‒OR 16、‒SR 17、‒C(=O)OR 18、芳基、雜芳基或‒Si(R 19) 3； R 15至R 19各自為C 4~C 30直鏈烷基、C 4~C 30支鏈烷基、C 4~C 30環烷基、C 4~C 30烯基或C 4~C 30炔基，且R 15至R 19各自為未經取代或經至少一個R 20取代； R 20為鹵素、‒CN或-SiR 21R 22R 23； R 21至R 23各自為C 1~C 30烷基； Ar為亞芳基或亞雜芳基； X與Z各自為‒CH 2‒或‒O‒；及 Y為C 1~C 20直鏈亞烷基、C 3~C 20支鏈亞烷基或C 3~C 20亞環烷基。 A non-fullerene electron acceptor material, comprising a repeating unit represented by the following formula (II): [Formula II]
Figure 03_image043
Wherein, R 1 is C 1 ~C 30 alkyl; D is
Figure 03_image045
,
Figure 03_image047
,
Figure 03_image049
,
Figure 03_image051
,
Figure 03_image053
,
Figure 03_image055
,
Figure 03_image057
,
Figure 03_image059
,
Figure 03_image061
,
Figure 03_image063
,
Figure 03_image065
,
Figure 03_image067
,
Figure 03_image069
or
Figure 03_image071
；
R 2 is hydrogen, C 1 to C 30 alkyl, C 1 to C 30 alkoxy, C 1 to C 30 alkyl aryl, or C 1 to C 30 alkyl heteroaryl; E is
Figure 03_image073
,
Figure 03_image075
,
Figure 03_image077
,
Figure 03_image079
,
Figure 03_image081
or
Figure 03_image083
；
R 3 is hydrogen, halogen, C 1 ~C 30 alkyl or C 1 ~C 30 alkoxy; L is
Figure 03_image206
,
Figure 03_image087
,
Figure 03_image089
,
Figure 03_image091
,
Figure 03_image093
or
Figure 03_image095
；
R 5 to R 14 are each hydrogen, fluorine, chlorine, R 15 , ‒CN, ‒OR 16 , ‒SR 17 , ‒C(=O)OR 18 , aryl, heteroaryl, or ‒Si(R 19 ) 3 ; R 15 to R 19 are each C 4 to C 30 linear alkyl, C 4 to C 30 branched alkyl, C 4 to C 30 cycloalkyl, C 4 to C 30 alkenyl or C 4 to C 30 Alkynyl, and R 15 to R 19 are each unsubstituted or substituted with at least one R 20 ; R 20 is halogen, ‒CN or -SiR 21 R 22 R 23 ; R 21 to R 23 are each C 1 to C 30 Alkyl; Ar is arylene or heteroarylene; X and Z are each ‒CH 2 ‒ or ‒O‒; and Y is C 1 ~C 20 linear alkylene, C 3 ~C 20 branched alkylene Alkyl group or C 3 ~C 20 cycloalkylene group. 如請求項8所述的非富勒烯電子受體材料，其中，D為
Figure 03_image105
或
Figure 03_image045
。 The non-fullerene electron acceptor material according to claim 8, wherein D is
Figure 03_image105
or
Figure 03_image045
. 一種有機光伏電池，包含一主動層，該主動層包括如請求項1或8所述的非富勒烯電子受體材料。An organic photovoltaic cell includes an active layer including the non-fullerene electron acceptor material according to claim 1 or 8.
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