WO2021136435A1 - 共轭聚合物给体材料及其制备方法和应用 - Google Patents

共轭聚合物给体材料及其制备方法和应用 Download PDF

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WO2021136435A1
WO2021136435A1 PCT/CN2020/141660 CN2020141660W WO2021136435A1 WO 2021136435 A1 WO2021136435 A1 WO 2021136435A1 CN 2020141660 W CN2020141660 W CN 2020141660W WO 2021136435 A1 WO2021136435 A1 WO 2021136435A1
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conjugated polymer
donor material
polymer donor
compound
reaction
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丁黎明
肖作
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国家纳米科学中心
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    • Y02E10/549—Organic PV cells

Definitions

  • This application relates to the field of organic solar cell preparation, in particular to a conjugated polymer donor material and its preparation method and application.
  • Organic solar cells use organic conjugated molecules as active materials, which have many advantages such as light weight, flexibility, wide raw material sources, solution processing and large-area preparation, and are one of the focuses of global academia and industry in recent years. .
  • using electron donor unit (D) and electron acceptor unit (A) to construct D-A conjugated polymer donor material is an effective way to improve battery energy conversion efficiency.
  • the ideal DA conjugated polymer donor material requires a relatively narrow optical band gap to absorb more photons.
  • the low HOMO energy level can ensure that the battery obtains a high open circuit voltage (Voc), and good crystallinity can achieve high Hole mobility and good compatibility with acceptor materials can form ideal nano-scale phase separation, thereby improving the energy conversion efficiency of the device.
  • Donor materials As one of the most important materials for the active layer of organic solar cells, donor materials have always been a hot research topic in the field of solar cells because of the variety of materials and the variety of structures.
  • Donor materials mainly include polymers and small molecules.
  • polymers are the most widely studied, mainly including the following categories: polyparaphenylene vinylene (PPV), polythiophene (P3HT) and D-A conjugated polymer series.
  • PV polyparaphenylene vinylene
  • P3HT polythiophene
  • D-A conjugated polymer series D-A conjugated polymer series.
  • conjugated molecular materials are the driving force for the improvement of the performance of organic solar cells.
  • many types of organic conjugated compounds including conjugated polymers, conjugated small molecules and fullerenes have been applied to battery activity. Floor.
  • PBDTfDTBT is a conjugated polymer donor, which can be represented by the following structural formula:
  • non-fullerene acceptor (NFA) materials With the rise of non-fullerene acceptor (NFA) materials in recent years, the development of non-fullerene molecular acceptors has shown the potential of non-fullerene systems in organic solar cells. The development of donor materials that can be used in conjunction with non-fullerenes has received renewed attention.
  • NFA non-fullerene acceptor
  • this application provides a conjugated polymer donor material and its preparation method and application.
  • the donor material provided by the present application has high hole mobility, and the organic solar cell obtained by using this material has high open circuit voltage and energy conversion efficiency.
  • this application adopts the following technical solutions:
  • the present application provides a conjugated polymer donor material, the conjugated polymer donor material has a structure as shown in Formula I:
  • X is selected from a fluorine atom or a chlorine atom
  • R 1 is selected from a C1-C5 alkyl group
  • R 2 is selected from a C6-C12 alkyl group
  • n is selected from an integer of 5-1000.
  • the introduction of fluorine or chlorine atoms at specific sites can enhance molecular dipoles and intermolecular interactions, increase the ⁇ - ⁇ stacking between the polymer backbone, and facilitate charge transport, thereby increasing hole mobility .
  • the length of the alkyl side chain of the polymer needs to be balanced to ensure that the arrangement between the polymers is more orderly. Therefore, the side chain closer to the polymer main chain, that is, R 2 needs to be longer, while The side chain farther from the main chain, that is, R 1 needs to be shorter, so as to ensure the balance of the length of the two side chains, which is more beneficial to the arrangement of the polymer, makes the stacking more orderly, and thus is more conducive to charge transport and improves the empty space. Hole mobility.
  • R 1 is selected from C1-C5 alkyl groups, for example, C1, C2, C3, C4 or C5 linear or branched alkyl groups
  • R 2 is selected from C6-C12 alkyl groups, for example, Is a C6, C7, C8, C9, C10, C11 or C12 linear or branched alkyl group
  • n is selected from an integer of 5 to 1000, for example, 5, 10, 50, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, or 1000.
  • the number average molecular weight of the conjugated polymer donor material is 60,000 to 80,000, for example, it can be 60,000, 62,000, 65,000, 68,000, 70,000, 72,000, 75,000, 78,000, or 80,000.
  • n in the conjugated polymer donor material is selected from an integer of 20-100, for example, it may be 20, 25, 30, 35, 40, 50, 60, 70, 80, 90 or 100.
  • the hole mobility of the conjugated polymer donor material is (1.1-1.8) ⁇ 10 -3 cm 2 /Vs, for example, it can be 1.1 ⁇ 10 -3 cm 2 /Vs, 1.2 ⁇ 10 -3 cm 2 / Vs, 1.3 ⁇ 10 -3 cm 2 / Vs, 1.4 ⁇ 10 -3 cm 2 / Vs, 1.5 ⁇ 10 -3 cm 2 / Vs, 1.6 ⁇ 10 -3 cm 2 / Vs, 1.7 ⁇ 10 -3 cm 2 /Vs or 1.8 ⁇ 10 -3 cm 2 /Vs, etc.
  • R 1 in the conjugated polymer donor material is -C 2 H 5 .
  • R 2 in the conjugated polymer donor material is -C 6 H 13 .
  • the conjugated polymer donor material has a structure as shown in formula II or formula III, wherein n is selected from an integer ranging from 5 to 1000.
  • the formula II is The structure is named D18.
  • the present application provides a method for preparing the conjugated polymer donor material as described in the first aspect, and the preparation method includes the following steps:
  • this method can be used to prepare the conjugated polymer donor material shown in formula I, where X can be a fluorine atom or a chlorine atom, but if X is a bromine atom or an iodine atom, it will interfere with the polymerization reaction. Occurs, a regular polymer cannot be formed, and the corresponding product cannot be obtained. At the same time, X cannot be substituted for another site on the thiophene ring alone.
  • the reaction in step (1) is carried out in the presence of a catalyst.
  • the catalyst used in the reaction in step (1) is tetrakistriphenylphosphine palladium.
  • the reaction in step (1) is carried out under a nitrogen atmosphere.
  • the solvent of the reaction in step (1) is toluene.
  • the reaction temperature in step (1) is 20-30°C, for example 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C or 30°C, etc.; the reaction time is 9-12h, for example, it can be 9h, 9.5h, 10h, 10.5h, 11h, 11.5h or 12h.
  • the catalyst in step (1) is tetrakistriphenylphosphine palladium Pd(PPh 3 ) 4 .
  • the reaction in step (2) is carried out under light-shielding conditions.
  • the polymerization reaction in step (3) is carried out under a nitrogen atmosphere.
  • the polymerization reaction in step (3) is carried out in the presence of a target catalyst.
  • the target catalyst is a combination of tris(dibenzylideneacetone) dipalladium Pd 2 (dba) 3 and tris(o-methylphenyl)phosphorus P(o-Tol) 3 .
  • the molar ratio of tris(dibenzylideneacetone)dipalladium and tris(o-methylphenyl)phosphorus in step (3) is 1:(3-6), for example, it can be 1:3, 1: 3.5, 1:4, 1:4.5, 1:5, 1:5.5 or 1:6, etc.
  • the polymerization temperature in step (3) is 100-120°C, for example, it can be 100°C, 102°C, 105°C, 110°C, 112°C, 115°C, 118°C or 120°C, etc.; the reaction time is 15°C -20h, for example, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h, 20h, etc.
  • the preparation method includes the following steps:
  • the present application also provides an organic solar cell, which includes an anode, a hole transport layer, an active material layer, an electron transport layer, and a cathode stacked in sequence; the active material layer includes an electron donor and The electron acceptor, and the electron donor is selected from the conjugated polymer donor material described in the first aspect.
  • the mass ratio of the electron donor and the electron acceptor is 1:(0.3-3), for example, it can be 1:0.3, 1:0.5, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8 or 1:3, etc.
  • the electron acceptor is a non-fullerene acceptor material.
  • the electron acceptor is selected from any one or both of non-fullerene acceptor Y6, non-fullerene acceptor IT4F, non-fullerene acceptor ITIC or non-fullerene acceptor Y6-BO A combination of more than one.
  • the conjugated polymer donor material for organic solar cells provided by this application has a higher hole mobility through the introduction of fluorine or chlorine atoms and a reasonable combination of alkyl side chains. It is well matched with non-fullerene receptors, and has good solubility and solution processing performance. It can be used to prepare organic solar cells, and the obtained organic solar cells have higher open circuit voltage and energy conversion efficiency;
  • the hole mobility of the conjugated polymer donor D18 provided by this application is increased by an order of magnitude, reaching 1.59 ⁇ 10 -3 cm 2 /Vs, which is more compatible with non-fullerene acceptor materials.
  • the organic solar cell is prepared by blending D18 and non-fullerene acceptor Y6 with an efficiency of 18.2%, which is the highest efficiency currently achieved by organic solar cells.
  • Fig. 1 is a proton nuclear magnetic resonance spectrum of the conjugated polymer donor material D18 synthesized in Example 1.
  • Fig. 3 is a current-voltage (J-V) curve of a hole-conducting device prepared from the conjugated polymer donor material D18 provided in Example 1.
  • FIG. 4 is a current-voltage (J-V) curve of a hole-conducting device prepared by formula III of the conjugated polymer donor material provided in Example 2.
  • FIG. 4 is a current-voltage (J-V) curve of a hole-conducting device prepared by formula III of the conjugated polymer donor material provided in Example 2.
  • Fig. 5 is a current-voltage (J-V) curve of a hole-conducting device prepared by the conjugated polymer donor material formula IV provided in Comparative Example 1.
  • Fig. 6 is the current-voltage (J-V) curve of the organic solar cell provided in Application Example 1.
  • Fig. 7 is the current-voltage (J-V) curve of the organic solar cell provided in Application Example 2.
  • FIG. 8 is the current-voltage (J-V) curve of the organic solar cell provided in Application Example 3.
  • FIG. 8 is the current-voltage (J-V) curve of the organic solar cell provided in Application Example 3.
  • Fig. 9 is a current-voltage (J-V) curve of the organic solar cell provided in Application Example 4.
  • FIG. 10 is the current-voltage (J-V) curve of the organic solar cell provided in Application Example 5.
  • Fig. 11 is the current-voltage (J-V) curve of the organic solar cell provided by Comparative Example 1.
  • FIG. 12 is an external quantum efficiency (EQE) curve of the organic solar cell provided in Application Example 1.
  • FIG. 12 is an external quantum efficiency (EQE) curve of the organic solar cell provided in Application Example 1.
  • the experimental methods used in the following examples are conventional methods unless otherwise specified.
  • the experimental materials and reagents used in the following experimental examples can be obtained through commercial channels or known experimental methods.
  • This embodiment provides a conjugated polymer donor material, the structural formula of which can be represented by Formula II, and the conjugated polymer donor material is named D18.
  • the specific preparation method is as follows:
  • the proton nuclear magnetic spectrum of conjugated polymer D18 is shown in Figure 1.
  • the nuclear magnetic data of D18 1 H NMR (CDCl 3 , 400MHz, ⁇ /ppm): 6.84 (broad peak, aromatic proton), 0.88-1.51 (broad peak, Aliphatic protons).
  • the number average molecular weight of D18 measured by gel exclusion chromatography (GPC) was 72,500, and the molecular weight distribution index (PDI) was 1.51.
  • Absorbance refers to the intensity of the incident light before the light passes through the solution or a substance and the intensity of the transmitted light after the light passes through the solution or substance. Based on the logarithm of the ratio at the base 10, Figure 2 shows that the absorption peaks of polymer D18 in the solution are 559nm and 584nm, and the absorption peaks in the film are 555nm and 581nm.
  • This embodiment provides a conjugated polymer donor material, the structure of which is represented by Formula III:
  • step (3) The steps (1) and (2) of the preparation method are the same as those in Example 1.
  • the specific operation of step (3) is as follows: Add compound 3 (70mg), (4,8-bis(5- (2-Ethylhexyl)-4chloro-thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(trimethylstannane) ) (75mg), Pd 2 (dba) 3 (2.12mg) and P(o-Tol) 3 (7.05mg), reacted at 110°C for 16h under the protection of nitrogen.
  • the nuclear magnetic data of formula III are: 1 H NMR (CDCl 3 , 400 MHz, ⁇ /ppm): 7.00 (broad peak, aromatic proton), 0.88-1.55 (broad peak, aliphatic proton).
  • the number-average molecular weight of formula III measured by gel exclusion chromatography (GPC) is 40800, and the molecular weight distribution index (PDI): 1.89; the absorption peaks of formula III in solution are 562nm and 590nm, and the absorption peak in the film is 558nm And 586nm.
  • This embodiment provides a conjugated polymer donor material, the structure of which is represented by formula IV:
  • step (3) The steps (1) and (2) of the preparation method are the same as those in Example 1.
  • the specific operation of step (3) is as follows: Add compound 3 (70mg), (4,8-bis(5- (2-Ethylhexyl)-3,4-difluoro-thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophen-2,6-diyl)bis(tri Methylstannane) (75.3mg), Pd 2 (dba) 3 (2.12mg) and P(o-Tol) 3 (7.05mg) were reacted at 110°C for 16h under the protection of nitrogen.
  • Nuclear magnetic data of formula III 1 H NMR (CDCl 3 , 400 MHz, ⁇ /ppm): 7.00 (broad peak, aromatic protons), 0.87-1.55 (broad peak, aliphatic protons).
  • the number average molecular weight of formula III is 51800 and the molecular weight distribution index (PDI) is 1.75 as measured by gel exclusion chromatography (GPC).
  • the absorption peaks of formula III in the solution are 550nm and 581nm, and the absorption peaks in the film are 549nm and 580nm.
  • the conjugated polymer donor materials provided in Examples 1-2 and Comparative Example 1 were prepared into hole-conducting devices based on the principle of space charge limited current (SCLC), which were used to measure the holes of each conjugated polymer donor material Mobility.
  • SCLC space charge limited current
  • the hole conduction device includes an ITO electrode, a PEDOT:PSS hole transport layer, an active material layer, a MoO 3 hole transport layer and an aluminum electrode stacked in sequence, and is used to measure the hole mobility of D18.
  • the preparation method is as follows:
  • ITO conductive glass
  • Example 2 The polymer material D18 provided in Example 1 was dissolved in chloroform to obtain a solution concentration of 4 mg/mL, and the solution was spin-coated on the PEDOT:PSS film, and dried to form an active layer with a thickness of 100 nm;
  • Al is vapor-deposited on the surface of the MoO 3 layer with a thickness of 100 nm to obtain the hole-conducting device.
  • ITO Indium Tin Oxides
  • PSS PSS is a polymer aqueous solution composed of PEDOT and PSS
  • PEDOT is a polymer of EDOT (3,4-ethylenedioxythiophene)
  • PSS is polystyrene sulfonate.
  • Example 3 The test results of the conjugated polymer donor material provided in Example 1 are shown in Figure 3. From the JV curve in the figure, the hole mobility of D18 provided in Example 1 can be obtained as 1.59 ⁇ 10 -3 cm 2 /Vs;
  • This application embodiment provides an organic solar cell, which includes an anode, a hole transport layer, an active material layer, an electron transport layer, and a cathode stacked in sequence, and the preparation method is as follows:
  • ITO conductive glass
  • PDIN is 2,9-bis(3-(dimethylamino)propyl)anthracene [2,1, 9-def: 6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraketone;
  • the organic solar cell is obtained by vapor-depositing Ag on the surface of the electron transport layer to form a cathode with a thickness of 80 nm.
  • This application example provides an organic solar cell, the preparation method of which is different from application example 1 only in step (2), which is specifically as follows:
  • This application example provides an organic solar cell, the preparation method of which is different from application example 1 only in step (2), which is specifically as follows:
  • Example 2 The polymer donor material D18 provided in Example 1 and the non-fullerene acceptor material ITIC were dissolved in chlorobenzene at a weight ratio of 1:3 to obtain a solution with a concentration of 15 mg/mL.
  • the solution was spin-coated on PEDOT: On the PSS film, an active layer is formed after drying, with a thickness of 100nm;
  • the ITIC structural formula is:
  • This application example provides an organic solar cell, the preparation method of which is different from application example 1 only in step (2), which is specifically as follows:
  • the IT4F structural formula is:
  • the light source is a 3A solar simulator based on a xenon lamp (Newport, Model: 91159A). Before testing, calibrate the light intensity with standard silicon solar cells (Enli SRC2020, 2cm ⁇ 2cm) (light intensity is AM 1.5G, 100mW/cm 2 ). Under the condition of 25°C, the batteries provided in Application Examples 1-5 and Application Comparative Example 1 were placed under a solar simulator, and the effective area of the battery was 4 mm 2 . The current-voltage (JV) curve of the battery was tested with a Keithley 2420 source meter, and the parameter settings: the voltage sweep range from -0.2V to 1.2V, and the sweep step size: 0.02V.
  • JV current-voltage
  • Application Example 1 Under AM 1.5G 100mW/cm 2 light intensity, the JV curve of the organic solar cell provided in Application Example 1 is shown in Figure 6.
  • the open circuit voltage of the organic solar cell is 0.859V
  • the short-circuit current density is 27.70mA/cm 2
  • the fill factor is 76.6%
  • the energy conversion efficiency is 18.22%. This is the first time that the efficiency of organic solar cells exceeds 18%.
  • Application Example 2 Under AM 1.5G 100mW/cm 2 light intensity, the JV curve of the organic solar cell provided in Application Example 2 is shown in Figure 7.
  • the open circuit voltage of the organic solar cell is 0.872V, and the short-circuit current density is 25.93mA/cm 2 , the fill factor is 77.2%, and the energy conversion efficiency is 17.46%.
  • Application Example 3 Under AM 1.5G 100mW/cm 2 light intensity, the JV curve of the organic solar cell provided in Application Example 3 is shown in Figure 8.
  • the open circuit voltage of the organic solar cell is 1.03V
  • the short-circuit current density is 15.11mA/cm 2
  • the fill factor is 72.5%
  • the energy conversion efficiency is 11.28%.
  • Application Example 4 Under AM 1.5G 100mW/cm 2 light intensity, the JV curve of the organic solar cell provided in Application Example 4 is shown in Figure 9.
  • the open circuit voltage of the organic solar cell is 0.89V, and the short-circuit current density is 23.05mA/cm 2 , the fill factor is 73.8%, and the energy conversion efficiency is 15.16%.
  • Application Example 5 Under AM 1.5G 100mW/cm 2 light intensity, the JV curve of the organic solar cell provided in Application Example 5 is shown in Figure 10.
  • the open circuit voltage of the organic solar cell is 0.888V
  • the short-circuit current density is 24.97mA/cm 2
  • the fill factor is 71.9%
  • the energy conversion efficiency is 15.94%.
  • Application Comparative Example 1 Under AM 1.5G 100mW/cm 2 light intensity, the JV curve of the organic solar cell provided by Application Comparative Example 1 is shown in Figure 11.
  • the open circuit voltage of the organic solar cell is 0.959V, and the short-circuit current density is 15.04mA/cm 2 , the fill factor is 67.3%, and the energy conversion efficiency is 9.71%.
  • the external quantum efficiency curve test of the organic solar cell is performed by the QE-R3011 (Enli Tech) test system. Before the test, a silicon detector (Enli Tech, Model: RS-S10-A) Calibrate the light intensity. Parameter setting: the wavelength scanning range is from 300 nm to 1100 nm, the scanning step length is 10 nm, and the test result of the application example 1 is shown in FIG. 12.
  • the conjugated polymer donor material provided by the present application has a higher hole mobility, and the hole mobility of D18 can reach 1.59 ⁇ 10 -3 cm 2 /Vs, and the donor material It has good compatibility with non-fullerene acceptor materials, so the prepared organic solar cell has better performance and high energy conversion rate.
  • the efficiency of organic solar cell prepared by blending D18 and Y6 is as high as 18.2%.

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Abstract

一种共轭聚合物给体材料及其制备方法和应用。所述共轭聚合物给体材料具有如式I所示的结构，其中，X选自氟原子或氯原子，R 1选自C1～C5的烷基，R 2选自C6～C12的烷基，n选自5～1000的整数。通过在特定的位点使用氟原子或氯原子进行取代，同时配合烷基链的合理选用，所得材料的空穴迁移率较高，可达1.59×10 -3cm 2/Vs，而且能与非富勒烯受体很好匹配，具有良好的溶解性和溶液加工性能，利用所述材料制备得到的有机太阳电池能量转换效率高。

Description

[根据细则37.2由ISA制定的发明名称]　共轭聚合物给体材料及其制备方法和应用 技术领域
本申请涉及有机太阳电池制备领域，尤其涉及一种共轭聚合物给体材料及其制备方法和应用。
背景技术
有机太阳电池(PSCs)以有机共轭分子为活性材料，具有质轻、柔性、原料来源广泛、可溶液加工和大面积制备等诸多优点，是近年来全球学术界和工业界关注的焦点之一。其中以电子给体单元(D)和电子受体单元(A)构筑D-A型共轭聚合物给体材料是提高电池能量转化效率的有效途径。理想的D-A共轭聚合物给体材料要求具有相对窄的光学带隙从而吸收更多的光子，低的HOMO能级可以保证电池获得高的开路电压(Voc)，好的结晶性可以实现高的空穴迁移率，与受体材料具有好的相容性可以形成理想的纳米尺度相分离，从而提高器件的能量转换效率。
作为有机太阳电池活性层最主要的材料之一，给体材料因为材料种类繁多、结构变幻多样一直是太阳能电池领域的热点研究课题。给体材料主要包括聚合物和小分子，其中聚合物研究最为广泛，主要包括以下几大类：聚对苯撑乙烯(PPV)类、聚噻吩类(P3HT)和D-A共轭聚合物系列类。其中，共轭分子材料的开发和不断进步是有机太阳电池性能提高的源动力，目前包括共轭高分子、共轭小分子和富勒烯等许多种类的有机共轭化合物已被应用到电池活性层。
PBDTfDTBT是一种共轭聚合物给体，可以由如下结构式表示：
Figure PCTCN2020141660-appb-000001
PBDTfDTBT与富勒烯受体PC71BM组合的有机太阳电池效率达6.02％，但由于该材料空穴迁移率不高，使用空间电荷限制电流法(SCLC)测得其空穴迁移率仅为1.53×10 -4cm 2/Vs，电池效率也不高，因此该材料目前没有看到相关后续研究。(参见Lee J,Sin D H,Clement J A,et al.Medium-Bandgap Conjugated Polymers Containing Fused Dithienobenzochalcogenadiazoles:Chalcogen Atom Effects on Organic Photovoltaics[J].Macromolecules,2016,49(24):9358–9370.)
随着近年来非富勒烯受体(Nonfullerene acceptor，NFA)材料的兴起，非富勒烯分子受体的开发向大家展示了非富勒烯体系在有机太阳电池中的应用潜力，相应的对于能够与非富勒烯配合使用的给体材料的研发重新得到了重视。
因此，研发一种能够与非富勒烯受体材料匹配的高空穴迁移率的聚合物给体材料成为本领域研究的热点。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
鉴于相关技术中存在的问题，本申请提供一种共轭聚合物给体材料及其制 备方法和应用。本申请提供的给体材料具有较高的空穴迁移率，利用此材料得到的有机太阳电池具有较高的开路电压以及能量转换效率。为达此目的，本申请采用如下技术方案：
第一方面，本申请提供一种共轭聚合物给体材料，所述共轭聚合物给体材料具有如式I所示的结构：
Figure PCTCN2020141660-appb-000002
其中，X选自氟原子或氯原子，R 1选自C1～C5的烷基，R 2选自C6～C12的烷基，n选自5～1000的整数。
本申请中，在特定位点上引入氟原子或氯原子，可以增强分子偶极和分子间相互作用，提高高分子主链间的π-π堆积，有利于电荷传输，从而提高空穴迁移率。同时，高分子的烷基侧链的长度需要保持均衡才能保证高分子之间的排列更加有序，因此离高分子主链较近的侧链，即R 2需要更长一些，而离高分子主链较远的侧链，即R 1需要更短一些，这样才能保证两种侧链的长度均衡，对高分子的排列更有利，使堆积更有序，从而更有利于电荷传输，提高空穴迁移 率。
本申请中，R 1选自C1～C5的烷基，例如可以是C1、C2、C3、C4或C5的直链或支链的烷基，R 2选自C6～C12的烷基，例如可以是C6、C7、C8、C9、C10、C11或C12的直链或支链的烷基，n选自5～1000的整数，例如可以是5、10、50、100、150、200、300、400、500、600、700、800、900或1000。
作为本申请一种优选的技术方案，所述共轭聚合物给体材料的数均分子量为60000～80000，例如可以是60000、62000、65000、68000、70000、72000、75000、78000或80000等。
优选地，所述共轭聚合物给体材料中n选自20～100的整数，例如可以是20、25、30、35、40、50、60、70、80、90或100等。
优选地，所述共轭聚合物给体材料的空穴迁移率为(1.1-1.8)×10 -3cm 2/Vs，例如可以是1.1×10 -3cm 2/Vs、1.2×10 -3cm 2/Vs、1.3×10 -3cm 2/Vs、1.4×10 -3cm 2/Vs、1.5×10 -3cm 2/Vs、1.6×10 -3cm 2/Vs、1.7×10 -3cm 2/Vs或1.8×10 -3cm 2/Vs等。
作为本申请一种优选的技术方案，所述共轭聚合物给体材料中R 1为-C 2H 5。
优选地，所述共轭聚合物给体材料中R 2为-C 6H 13。
作为本申请一种优选的技术方案，所述共轭聚合物给体材料具有如式II或式III所示的结构，其中，n选自5～1000的整数，本申请中，将式II所示结构命名为D18。
Figure PCTCN2020141660-appb-000003
第二方面，本申请提供一种如第一方面所述的共轭聚合物给体材料的制备方法，所述制备方法包括如下步骤：
(1)将化合物1和4-(2-烷基己基)噻吩-2-三丁基锡混合反应，分离得到化合物2，该反应可由如下反应式表示：
Figure PCTCN2020141660-appb-000004
(2)将所述化合物2和N-溴代琥珀酰亚胺(NBS)混合反应，分离得到化合物3，该反应可由如下反应式表示：
Figure PCTCN2020141660-appb-000005
(3)将化合物3和(4,8-双(5-(2-烷基己基)-4卤代-噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)混合发生聚合反应，分离后得到所述共轭聚合物给体材料；
Figure PCTCN2020141660-appb-000006
本申请中，使用此方法可以制备得到式I所示的共轭聚合物给体材料，其中X可以为氟原子或氯原子，但是，若X为溴原子或碘原子，则会干扰聚合反应的发生，无法生成规整的聚合物，得不到相应的产物，同时X也无法单独取代于噻吩环上的另一位点。
作为本申请一种优选的技术方案，步骤(1)所述反应在催化剂存在下进行。
优选地，步骤(1)所述反应使用的催化剂为四三苯基膦钯。
优选地，步骤(1)所述反应在氮气保护气氛下进行。
优选地，步骤(1)所述反应的溶剂为甲苯。
优选地，步骤(1)所述反应温度为20～30℃，例如可以是20℃、21℃、22℃、23℃、24℃、25℃、26℃、27℃、28℃、29℃或30℃等；反应时间为9～12h，例如可以是9h、9.5h、10h、10.5h、11h、11.5h或12h等。
优选地，步骤(1)所述催化剂为四三苯基膦钯Pd(PPh 3) 4。
优选地，步骤(2)所述反应在避光条件下进行。
作为本申请一种优选的技术方案，步骤(3)所述聚合反应在氮气保护气氛下进行。
优选地，步骤(3)所述聚合反应在靶类催化剂存在下进行。
优选地，所述靶类催化剂为三(二亚苄基丙酮)二钯Pd 2(dba) 3和三(邻甲基苯基)磷P(o-Tol) 3的组合。
优选地，步骤(3)所述三(二亚苄基丙酮)二钯和三(邻甲基苯基)磷的摩尔比为1:(3-6)，例如可以是1:3、1:3.5、1:4、1:4.5、1:5、1:5.5或1:6等。
优选地，步骤(3)所述聚合反应温度为100-120℃，例如可以是100℃、102℃、105℃、110℃、112℃、115℃、118℃或120℃等；反应时间为15-20h，例如可以是15h、15.5h、16h、16.5h、17h、17.5h、18h、18.5h、19h、19.5h或20h等。
作为本申请一种优选的技术方案，所述制备方法包括如下步骤：
(1)将化合物1、4-(2-烷基己基)噻吩-2-三丁基锡、四三苯基膦钯和甲苯混合，在氮气保护下20～30℃反应9～12h，旋蒸、萃取并洗脱后得到化合物2；
(2)将所述化合物2、N-溴代琥珀酰亚胺和氯仿混合，20～30℃下避光反应1～2h，旋蒸并洗脱后得到化合物3；
(3)将所述化合物3、(4,8-双(5-(2-烷基己基)-4卤代-噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)、三(二亚苄基丙酮)二钯和三(邻甲基苯基)磷混合，在氮气保护下100-120℃反应15-20h，沉析、抽提并层析得到所述共轭聚合物给体材料。
第三方面，本申请还提供一种有机太阳电池，所述有机太阳电池包括依次层叠的阳极、空穴传输层、活性材料层、电子传输层和阴极；所述活性材料层包括电子给体和电子受体，所述电子给体选自第一方面所述共轭聚合物给体材料。
作为本申请一种优选的技术方案，所述电子给体和电子受体的质量比为 1:(0.3-3)，例如可以是1:0.3、1:0.5、1:1、1:1.2、1:1.5、1:1.8、1:2、1:2.2、1:2.5、1:2.8或1:3等。
优选地，所述电子受体为非富勒烯受体材料。
优选地，所述电子受体选自非富勒烯受体Y6、非富勒烯受体IT4F、非富勒烯受体ITIC或非富勒烯受体Y6-BO中的任意一种或两种以上的组合。
本申请所述的数值范围不仅包括上述例举的点值，还包括没有列举出的上述数值范围之间的任意的点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
与相关技术相比，本申请至少具有以下有益效果：
(1)本申请提供的用于有机太阳电池的共轭聚合物给体材料，通过氟原子或氯原子的引入和烷基侧链的合理搭配，使其具有较高的空穴迁移率，能与非富勒烯受体很好匹配，同时具有良好的溶解性和溶液加工性能，能用于制备有机太阳电池，所得有机太阳电池具有较高的开路电压和能量转换效率；
(2)本申请提供的共轭聚合物给体D18，其空穴迁移率相比PBDTfDTBT提高了一个数量级，达到1.59×10 -3cm 2/Vs，更加匹配非富勒烯受体材料，进一步将D18与非富勒烯受体Y6共混制备有机太阳电池，效率达18.2％，是目前有机太阳电池取得的最高效率。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
图1为实施例1合成的共轭聚合物给体材料D18的核磁共振氢谱。
图2为实施例1合成的共轭聚合物给体材料D18在溶液和薄膜中的吸收光谱。
图3为实施例1提供的共轭聚合物给体材料D18制备的空穴传导器件的电 流-电压(J-V)曲线。
图4为实施例2提供的共轭聚合物给体材料式III制备的空穴传导器件的电流-电压(J-V)曲线。
图5为对比例1提供的共轭聚合物给体材料式IV制备的空穴传导器件的电流-电压(J-V)曲线。
图6为应用实施例1提供的有机太阳电池的电流-电压(J-V)曲线。
图7为应用实施例2提供的有机太阳电池的电流-电压(J-V)曲线。
图8为应用实施例3提供的有机太阳电池的电流-电压(J-V)曲线。
图9为应用实施例4提供的有机太阳电池的电流-电压(J-V)曲线。
图10为应用实施例5提供的有机太阳电池的电流-电压(J-V)曲线。
图11为应用对比例1提供的有机太阳电池的电流-电压(J-V)曲线。
图12为应用实施例1提供的有机太阳电池的外量子效率(EQE)曲线。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本申请的技术方案，但下述的实例仅仅是本申请的简易例子，并不代表或限制本申请的权利保护范围，本申请的保护范围以权利要求书为准。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。下述实验例中所使用的实验材料、试剂等均可通过商业途径或已知实验方法获得。
实施例1
本实施例提供一种共轭聚合物给体材料，其结构式可由式II表示，并将该共轭聚合物给体材料命名为D18。
Figure PCTCN2020141660-appb-000007
具体制备方法如下：
(1)化合物2的合成，该反应可由如下反应式表示：
Figure PCTCN2020141660-appb-000008
在100mL Schlenck管中依次加入化合物1(406mg)、4-(2-丁基辛基)噻吩-2-三丁基锡试剂(1.3g)、四三苯基膦钯Pd(PPh 3) 4(115.6mg)、甲苯溶液(30mL)，氮气保护室温回流过夜。减压旋蒸除掉甲苯后，用石油醚萃取，粗产品用柱层析提纯，使用体积比为1:1的二氯甲烷和石油醚的混合溶剂作为洗脱剂，得到橙黄色油状产物化合物2共计696mg，产率为93％。
其中化合物2的核磁与质谱数据为： 1H NMR(CDCl 3,400MHz,δ/ppm):8.01(s,2H),7.15(s,2H),6.90(s,2H),2.57(d,J＝6.8Hz,4H),1.65-1.64(m,2H),1.35-1.29(m,32H),0.92-0.86(m,12H). 13C NMR(101MHz,CDCl 3)δ150.09,143.13,137.59,135.80,133.19,129.31,126.79,121.40,119.10,38.82,34.94,33.31,33.00,31.93,29.71,28.86,26.60,23.07,22.71,14.18,14.14.ESI-HRMS(m/z):C 42H 56N 2S 5 calc.748.30,found 748.30(M +)。
(2)化合物3的合成，该反应可由如下反应式表示：
Figure PCTCN2020141660-appb-000009
在50mL单口瓶中依次加入化合物2(374mg)、N-溴代琥珀酰亚胺(NBS)(178mg)和氯仿(30mL)，常温避光反应1小时。减压旋蒸除掉氯仿，粗产品用柱层析提纯，使用体积比为1:2的二氯甲烷和石油醚的混合溶剂作为洗脱剂，得到橙黄色固体化合物3共计436mg，使用xxx测得其产率为90％。
化合物3的核磁与质谱数据为： 1H NMR(CDCl 3,400MHz,δ/ppm)：7.91(s,2H),6.98(s,2H),2.51(d,J＝7.1Hz,4H),1.72-1.70(s,2H),1.32-1.29(m,32H),0.93-0.87(m,12H). 13C NMR(101MHz,CDCl 3)δ：149.69,142.43,136.49,135.46,132.76,129.14,126.01,119.04,110.15,38.51,34.19,33.33,33.03,31.94,29.74,28.77,26.51,23.10,22.73,14.18.ESI-HRMS(m/z):C 42H 54Br 2N 2S 5 calc.904.13,found 904.13(M +)。
(3)D-A型共轭聚合物D18的合成，该反应可由如下反应式表示：
Figure PCTCN2020141660-appb-000010
在10mL Schlenck管中依次加入化合物3(70mg)、(4,8-双(5-(2-乙基己基)-4氟-噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)(72.6mg)、三(二亚苄基丙酮)二钯Pd 2(dba) 3(2.12mg)和三(邻甲基苯基)磷P(o-Tol) 3(7.05mg)，在氮气保护下110℃反应16h。冷却至室温后反应液逐滴加到150mL甲醇中沉析，滤出沉淀物得到粗产物，将粗产品转移至索氏提取器中，依次用二氯甲烷，氯仿和氯苯进行抽提，浓缩得到的氯苯提取物，并将其滴入至甲醇中进行再次层析，最后得到红褐色固体产物D18(80mg，产率76％)。
共轭聚合物D18的核磁氢谱如图1所示，D18的核磁数据： 1H NMR(CDCl 3,400MHz,δ/ppm)：6.84(宽峰，芳香质子)，0.88-1.51(宽峰，脂肪族质子)。用凝胶排阻色谱(GPC)测得D18的数均分子量为72500，分子量分布指数(PDI)：1.51。
将D18溶于氯仿中，浓度为0.01mg/mL，检测D18在溶液中的紫外-可见吸收光谱；将D18溶于氯仿中，浓度为4mg/mL，旋涂到玻璃基底上烘干后形成的D18薄膜，厚度为100nm，检测D18薄膜的紫外-可见吸收光谱，D18在 溶液和薄膜中的紫外-可见吸收光谱如图2所示，其中D18-S代表共轭聚合物D18在溶液中的紫外-可见吸收光谱，D18-F代表D18在薄膜中的紫外-可见吸收光谱，吸光度(Absorbance)是指光线通过溶液或某一物质前的入射光强度与该光线通过溶液或物质后的透射光强度比值的以10为底的对数，由图2得出聚合物D18在溶液中的吸收峰为559nm和584nm，在薄膜中的吸收峰为555nm和581nm。
实施例2
本实施例提供一种共轭聚合物给体材料，其结构由式III表示：
Figure PCTCN2020141660-appb-000011
其制备方法中步骤(1)和步骤(2)与实施例1相同，步骤(3)的具体操作如下：在10mL Schlenck管中依次加入化合物3(70mg)、(4,8-双(5-(2-乙基己基)-4氯-噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)(75mg)、Pd 2(dba) 3(2.12mg)和P(o-Tol) 3(7.05mg)，在氮气保护下110℃反应16h。冷却至室温后反应液逐滴加到150mL甲醇中沉析，滤出沉淀物得到粗产物，将粗产品转移至索氏提取器中，依次用二氯甲烷，氯仿进行抽提，浓缩得到的氯仿 提取物，并将其滴入至甲醇中进行再次层析，最后得到红褐色固体产物式III(73mg，产率68％)。
Figure PCTCN2020141660-appb-000012
式III的核磁数据为： 1H NMR(CDCl 3，400MHz，δ/ppm)：7.00(宽峰，芳香质子)，0.88-1.55(宽峰，脂肪族质子)。用凝胶排阻色谱(GPC)测得式III的数均分子量为40800，分子量分布指数(PDI)：1.89；式III在溶液中的吸收峰为562nm和590nm，在薄膜中的吸收峰为558nm和586nm。
对比例1
本实施例提供一种共轭聚合物给体材料，其结构由式IV表示：
Figure PCTCN2020141660-appb-000013
其制备方法中步骤(1)和步骤(2)与实施例1相同，步骤(3)的具体操作如下：在10mL Schlenck管中依次加入化合物3(70mg)、(4,8-双(5-(2-乙基己基)-3,4-二氟-噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)(75.3mg)、Pd 2(dba) 3(2.12mg)和P(o-Tol) 3(7.05mg)，在氮气保护下110℃反应16h。冷却至室温后反应液逐滴加到150mL甲醇中沉析，滤出沉淀物得到粗产物，将粗产品转移至索氏提取器中，依次用二氯甲烷，氯仿和氯苯进行抽提，浓缩得到的氯苯提取物，并将其滴入至甲醇中进行再次层析，最后得到红褐色固体产物式IV(78mg，产率72％)。
Figure PCTCN2020141660-appb-000014
式III的核磁数据： 1H NMR(CDCl 3,400MHz,δ/ppm)：7.00(宽峰，芳香质子)，0.87-1.55(宽峰，脂肪族质子)。用凝胶排阻色谱(GPC)测得式III的数均分子量为51800，分子量分布指数(PDI)：1.75。式III在溶液中的吸收峰为550nm和581nm，在薄膜中的吸收峰为549nm和580nm。
试验例1
将实施例1-2与对比例1提供的共轭聚合物给体材料制备成基于空间电荷限制电流(SCLC)原理的空穴传导器件，用于测量各个共轭聚合物给体材料的空穴迁移率。
空穴传导器件包括依次层叠的ITO电极、PEDOT:PSS空穴传输层、活性材料层、MoO 3空穴传输层和铝电极，用于测量D18空穴迁移率，其制备方法如下：
(1)在清洗干净的导电玻璃(ITO)基底上旋涂PEDOT:PSS溶液(PEDOT:PSS质量比＝1:6)，150℃加热10分钟，形成PEDOT:PSS膜，作为空穴传输层，厚度为30nm；
(2)将实施例1提供的聚合物材料D18溶于氯仿，得到溶液的浓度为4mg/mL，将该溶液旋涂于PEDOT:PSS膜上，烘干后形成活性层，厚度为100nm；
(3)将MoO 3蒸镀到D18表面，厚度为6nm；
(4)将Al蒸镀到MoO 3层表面，厚度为100nm，即得所述空穴传导器件。
其中，ITO(Indium Tin Oxides)为氧化铟锡；PEDOT:PSS是一种高分子的水溶液，由PEDOT和PSS两种物质构成，PEDOT为EDOT(3,4-乙撑二氧噻吩)的聚合物，PSS为聚苯乙烯磺酸盐。
电流-电压曲线测试：在室温条件下，将空穴传导器件放在暗态下扫描电流-电压曲线，器件有效面积为4mm 2。电流-电压(J-V)曲线用Keithley 2420源表测试，参数设置：电压扫描范围从0V到5V，扫描步长：0.02V。
实施例1提供的共轭聚合物给体材料测试结果如图3所示，从图中J-V曲线可以得到实施例1提供的D18的空穴迁移率为1.59×10 -3cm 2/Vs；
实施例2提供的共轭聚合物给体材料测试结果如图4所示，从图中J-V曲线可以得到实施例2提供的式III的空穴迁移率为1.10×10 -3cm 2/Vs；
对比例1提供的共轭聚合物给体材料测试结果如图5所示，从图中J-V曲线可以得到对比例1提供的式IV的空穴迁移率为7.28×10 -4cm 2/Vs。
应用实施例1
本应用实施例提供一种有机太阳电池，包括依次层叠的阳极、空穴传输层、活性材料层、电子传输层和阴极，其制备方法如下：
(1)在清洗干净的导电玻璃(ITO，作为阳极)基底上旋涂PEDOT:PSS溶液(PEDOT:PSS的质量比＝1:6)，150℃加热10分钟，形成PEDOT:PSS膜，作为空穴传输层，厚度为30nm；
(2)将实施例1提供的共轭聚合物给体材料D18和非富勒烯受体材料Y6按重量比1:1.6溶于氯仿，得到溶液的浓度为13mg/mL，将该溶液旋涂于PEDOT:PSS膜上，烘干后形成活性层，厚度为110nm；
(3)在活性层上旋涂PDIN溶液，烘干后形成电子传输层，厚度为3nm，其中，PDIN为2,9-双(3-(二甲氨基)丙基)蒽[2,1,9-def:6,5,10-d'e'f']二异喹啉-1,3,8,10(2H,9H)-四酮；
(4)将Ag蒸镀到电子传输层表面，形成阴极，厚度为80nm，即得所述有机太阳电池。
其中，Y6结构式为：
Figure PCTCN2020141660-appb-000015
应用实施例2
本应用实施例提供一种有机太阳电池，其制备方法与应用实施例1的区别仅在于步骤(2)不同，具体如下：
(2)将实施例1提供的高分子给体材料D18和非富勒烯受体材料Y6-BO按重量比1:2溶于氯仿，得到溶液的浓度为14mg/mL，将该溶液旋涂于PEDOT:PSS膜上，烘干后形成活性层，厚度为120nm；
其中，Y6-BO结构式为：
Figure PCTCN2020141660-appb-000016
应用实施例3
本应用实施例提供一种有机太阳电池，其制备方法与应用实施例1的区别仅在于步骤(2)不同，具体如下：
(2)将实施例1提供的高分子给体材料D18和非富勒烯受体材料ITIC按重量比1:3溶于氯苯，得到溶液的浓度为15mg/mL，将该溶液旋涂于PEDOT:PSS膜上，烘干后形成活性层，厚度为100nm；
其中，ITIC结构式为：
Figure PCTCN2020141660-appb-000017
应用实施例4
本应用实施例提供一种有机太阳电池，其制备方法与应用实施例1的区别仅在于步骤(2)不同，具体如下：
(2)将实施例1提供的高分子给体材料D18和非富勒烯受体材料IT4F按重量比3:1溶于氯苯，得到溶液的浓度为8mg/mL，将该溶液旋涂于PEDOT:PSS膜上，烘干后形成活性层，厚度为100nm；
IT4F结构式为：
Figure PCTCN2020141660-appb-000018
应用实施例5
与应用实验例1的区别在于，将共轭聚合物给体材料D18替换为实施例2提供的共轭聚合物给体材料，其余条件及制备方法同应用实施例1。
应用对比例1
与应用实验例1的区别在于，将共轭聚合物给体材料D18替换为对比例1提供的共轭聚合物给体材料，其余条件及制备方法同应用实施例1。
试验例2
对应用实施例1-5提供的有机太阳电池进行电流-电压曲线测试
光源是基于氙灯的3A级太阳光模拟器(Newport，Model：91159A)。测试前先用标准硅太阳电池(Enli SRC2020，2cm×2cm)对光强进行校准(光强为AM 1.5G，100mW/cm 2)。在25℃条件下，将应用实施例1-5与应用对比例1提供的电池放在太阳光模拟器下进行，电池有效面积为4mm 2。电池的电流-电压 (J-V)曲线用Keithley 2420源表测试，参数设置：电压扫描范围从-0.2V到1.2V，扫描步长：0.02V。
应用实施例1：在AM 1.5G 100mW/cm 2光强下，应用实施例1提供的有机太阳电池的J-V曲线如图6所示，该有机太阳电池的开路电压为0.859V，短路电流密度为27.70mA/cm 2，填充因子为76.6％，能量转换效率为18.22％，这是目前有机太阳电池效率首次超过18％。
应用实施例2：在AM 1.5G 100mW/cm 2光强下，应用实施例2提供的有机太阳电池的J-V曲线如图7所示，该有机太阳电池的开路电压为0.872V，短路电流密度为25.93mA/cm 2，填充因子为77.2％，能量转换效率为17.46％。
应用实施例3：在AM 1.5G 100mW/cm 2光强下，应用实施例3提供的有机太阳电池的J-V曲线如图8所示，该有机太阳电池的开路电压为1.03V，短路电流密度为15.11mA/cm 2，填充因子为72.5％，能量转换效率为11.28％。
应用实施例4：在AM 1.5G 100mW/cm 2光强下，应用实施例4提供的有机太阳电池的J-V曲线如图9所示，该有机太阳电池的开路电压为0.89V，短路电流密度为23.05mA/cm 2，填充因子为73.8％，能量转换效率为15.16％。
应用实施例5：在AM 1.5G 100mW/cm 2光强下，应用实施例5提供的有机太阳电池的J-V曲线如图10所示，该有机太阳电池的开路电压为0.888V，短路电流密度为24.97mA/cm 2，填充因子为71.9％，能量转换效率为15.94％。
应用对比例1：在AM 1.5G 100mW/cm 2光强下，应用对比例1提供的有机太阳电池的J-V曲线如图11所示，该有机太阳电池的开路电压为0.959V，短路电流密度为15.04mA/cm 2，填充因子为67.3％，能量转换效率为9.71％。
试验例3
电池外量子效率(EQE)曲线测试
由于应用实施例1提供的有机太阳电池能量转换效率最高，所以对该有机太阳电池进行电池外量子效率曲线测试，由QE-R3011(Enli Tech)测试系统测试，测试前需要用硅探测器(Enli Tech，Model：RS-S10-A)对光强进行校准。参数设置：波长扫描范围从300nm到1100nm，扫描步长：10nm，应用实施例1的测试结果如图12所示。
由图12可以看出应用实施例1提供的有机太阳电池的EQE响应在500nm处达到87％，这是目前为数不多的EQE响应能达到87％的有机太阳电池。
综上所述，本申请提供的共轭聚合物给体材料具有较高的空穴迁移率，且D18的空穴迁移率可达1.59×10 -3cm 2/Vs，并且所述给体材料与非富勒烯受体材料有较好的相容性，因此制得的有机太阳电池性能较好，能量转换率高，其中由D18与Y6共混制备的有机太阳电池效率高达18.2％。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，均落在本申请的保护范围和公开范围之内。

Claims (13)

  1. 一种共轭聚合物给体材料，其中，所述共轭聚合物给体材料具有如式I所示的结构：
    Figure PCTCN2020141660-appb-100001
    其中，X选自氟原子或氯原子，R 1选自C1～C5的烷基，R 2选自C6～C12的烷基，n选自5～1000的整数。
  2. 根据权利要求1所述的共轭聚合物给体材料，其中，所述共轭聚合物给体材料的数均分子量为65000～75000。
  3. 根据权利要求2所述的共轭聚合物给体材料，其中，所述共轭聚合物给体材料中n选自20～100的整数。
  4. 根据权利要求2所述的共轭聚合物给体材料，其中，所述共轭聚合物给体材料的空穴迁移率为(1.1～1.8)×10 -3cm 2/Vs。
  5. 根据权利要求1-4中任一项所述的共轭聚合物给体材料，其中，所述共轭聚合物给体材料中R 1为-C 2H 5。
  6. 根据权利要求5所述的共轭聚合物给体材料，其中，所述共轭聚合物给体材料中R 2为-C 6H 13。
  7. 根据权利要求1-6任一项所述的共轭聚合物给体材料，其中，所述共轭聚合物给体材料具有如式II或式III所示的结构，其中，n选自5～1000的整数，
    Figure PCTCN2020141660-appb-100002
  8. 一种如权利要求1-7任一项所述的共轭聚合物给体材料的制备方法，所述制备方法包括如下步骤：
    (1)将化合物1和4-(2-烷基己基)噻吩-2-三丁基锡混合反应，分离得到化合物2，所述化合物1和化合物2的结构式如下：
    Figure PCTCN2020141660-appb-100003
    (2)将所述化合物2和N-溴代琥珀酰亚胺混合反应，分离得到化合物3，所述化合物3的结构式如下：
    Figure PCTCN2020141660-appb-100004
    (3)将所述化合物3和(4,8-双(5-(2-烷基己基)-4卤代-噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)混合发生聚合反应，分离后得到所述共轭聚合物给体材料。
  9. 根据权利要求8所述的制备方法，其中，步骤(1)所述反应在催化剂存在下进行；
    优选地，步骤(1)所述反应使用的催化剂为四三苯基膦钯；
    优选地，步骤(1)所述反应在氮气保护气氛下进行；
    优选地，步骤(1)所述反应的溶剂为甲苯；
    优选地，步骤(1)所述反应温度为20～30℃，反应时间为9～12h；
    优选地，步骤(2)所述反应在避光条件下进行。
  10. 根据权利要求8或9所述的制备方法，其中，步骤(3)所述聚合反应在氮气保护气氛下进行；
    优选地，步骤(3)所述聚合反应在靶类催化剂存在下进行；
    优选地，所述靶类催化剂为三(二亚苄基丙酮)二钯和三(邻甲基苯基)磷的组合；
    优选地，步骤(3)所述三(二亚苄基丙酮)二钯和三(邻甲基苯基)磷的摩尔比为1:(3-6)；
    优选地，步骤(3)所述聚合反应温度为100-120℃，反应时间为15-20h。
  11. 根据权利要求8-10任一项所述的制备方法，其中，所述制备方法包括如下步骤：
    (1)将化合物1、4-(2-烷基己基)噻吩-2-三丁基锡、四三苯基膦钯和甲苯混合，在氮气保护下20～30℃反应9～12h，旋蒸、萃取并洗脱后得到化合物2；
    (2)将所述化合物2、N-溴代琥珀酰亚胺和氯仿混合，20～30℃下避光反应1～2h，旋蒸并洗脱后得到化合物3；
    (3)将所述化合物3、(4,8-双(5-(2-烷基己基)-4卤代-噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)、三(二亚苄基丙酮)二钯和三(邻甲 基苯基)磷混合，在氮气保护下100-120℃反应15-20h，沉析、抽提并层析得到所述共轭聚合物给体材料。
  12. 一种有机太阳电池，其中，所述有机太阳电池包括依次层叠的阳极、空穴传输层、活性材料层、电子传输层和阴极；
    所述活性材料层包括电子给体和电子受体，所述电子给体选自权利要求1～7任一项所述共轭聚合物给体材料。
  13. 根据权利要求12所述的有机太阳电池，其中，所述电子给体和电子受体的质量比为1:(0.3-3)；
    优选地，所述电子受体为非富勒烯受体材料；
    优选地，所述电子受体选自非富勒烯受体Y6、非富勒烯受体IT4F、非富勒烯受体ITIC或非富勒烯受体Y6-BO中的任意一种或两种以上的组合。
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