WO2016141862A1 - 一种电子传输层材料及其应用 - Google Patents

一种电子传输层材料及其应用 Download PDF

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WO2016141862A1
WO2016141862A1 PCT/CN2016/075708 CN2016075708W WO2016141862A1 WO 2016141862 A1 WO2016141862 A1 WO 2016141862A1 CN 2016075708 W CN2016075708 W CN 2016075708W WO 2016141862 A1 WO2016141862 A1 WO 2016141862A1
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group
atom
electron transport
transport layer
carbon atoms
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黄飞
孙辰
吴志鸿
叶轩立
曹镛
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority claimed from CN201510100372.6A external-priority patent/CN104788649B/zh
Priority claimed from CN201510145506.6A external-priority patent/CN104725613B/zh
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Priority to US15/550,514 priority Critical patent/US20180033985A1/en
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Definitions

  • the invention belongs to the technical field of optoelectronic devices, and in particular relates to an electron transport layer material and an application thereof.
  • conjugated polyelectrolytes and their neutral precursors are a very good class of electron transport layers [Chem. Mater. 2004, 16, 708; J. Am. Chem. Soc. 2004, 126, 9845-9853; Chinese patent ZL200310117518 .5], such conjugated polyelectrolyte materials can be used not only as light-emitting devices, but also as an interface modification layer to greatly improve the performance of organic solar cells, field effect transistors and perovskite solar cells [Chem.Soc.Rev.2010 , 39, 2500].
  • conjugated polyelectrolyte materials have a lower minimum unoccupied orbital (LUMO) energy level and a lower electron mobility, making the optimum thickness of such materials in photovoltaic devices only 5 nm, which is a requirement for device processing. More demanding.
  • LUMO minimum unoccupied orbital
  • the primary object of the present invention is to provide an electron transport layer material, which greatly improves the open circuit voltage and device performance of the solar cell.
  • An electron transport layer material having the following structure:
  • n is a natural number from 1 to 10000
  • B is a strong polar group
  • A1 and A2 are the same or different aromatic ring derivatives or a conjugated unit containing a carbon-carbon double bond or a carbon-nitrogen bond
  • M is A2 and B.
  • M is an alkyl group having 1 to 20 carbon atoms, or one or more carbon atoms on the alkyl group are one or more functional groups in an oxygen atom, an alkenyl group, an alkynyl group, an aryl group or an ester group.
  • the hydrogen atom is substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the above functional group.
  • the strongly polar group is one or more of an amine group, a quaternary ammonium salt group, a phosphate group, a phosphate group, a sulfonate group, a carboxyl group, and a hydroxyl group.
  • R is an alkyl group having 1 to 20 carbon atoms, or one or more carbon atoms on the alkyl group are one of an oxygen atom, an alkenyl group, an alkynyl group, an aryl group or an ester group.
  • the hydrogen atom is substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the above functional group;
  • the A1 is Wherein n is a natural number from 1 to 3, R is an alkyl group having 1 to 20 carbon atoms, or one or more carbon atoms on the alkyl group are one of an oxygen atom, an alkenyl group, an alkynyl group, an aryl group or an ester group.
  • the above functional group is substituted, and the hydrogen atom is substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the above functional group; and the A2 is one or more of the following structures:
  • R is an alkyl group having 1 to 20 carbon atoms, or one or more carbon atoms on the alkyl group are one of an oxygen atom, an alkenyl group, an alkynyl group, an aryl group or an ester group.
  • the hydrogen atom is substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the above functional group;
  • the material of the electron transporting layer can be prepared by first mixing an equimolar amount of a polar group-containing A2 monomer and a naphthyleneimide ring in an equimolar amount. Obtaining a polymer having a polar group which is not ionized under the action of an organic base and a palladium catalyst, and then subjecting the obtained polymer to a salting reaction at room temperature in the dark to obtain a polar group ionized polymer, and then further The obtained ionized polymer is treated with an ion exchange resin containing different counter ions, and then separated to obtain the electron transport layer material.
  • the present invention has the following advantages and beneficial effects:
  • the present invention applies a conjugated polymer containing a strong polar group to an electron transport layer material, and a polymer having a strong polar group side chain serves a significant cathode interface modification effect and enhances carriers.
  • the transmission capability has achieved better device performance.
  • a conjugated polymer material containing an electron withdrawing group such as a naphthalene diimide ring has a LUMO energy level matched with an electron acceptor material in the active layer, and thus is more advantageous for electrons to be affected by the active layer.
  • the bulk material is transferred into the electron transport layer. It can be used as an electron transport layer with good charge transport capability in optoelectronic devices such as luminescence and photovoltaics to improve the processing technology and performance of the device.
  • Figure 1 is a Fourier infrared absorption spectrum of the polymer obtained in Examples 1-4, wherein a is a Fourier infrared absorption spectrum of the polymers PNDIT-F6N, PNDIT-F6N-I, PNDIT-F6N-OH; Fourier infrared absorption spectra of PNDIT-F3N, PNDIT-F3N-I, PNDIT-F3N-OH.
  • Figure 2 is a graph showing the thermogravimetric analysis of the polymers obtained in Examples 1-4.
  • Figure 3 is a graph showing the absorption spectrum of the polymer obtained in Examples 1-4 in a methanol solution.
  • Figure 4 is a graph showing the absorption spectrum of a film of the polymer obtained in Examples 1-4.
  • Figure 5 is a graph comparing the reduction potential curves of the polymers obtained in Examples 1-4.
  • Fig. 6 is a graph showing the oxidation potential curves of the polymers obtained in Examples 1-4.
  • Figure 7 is a J-V graph of an organic solar cell device prepared by using the polymer obtained in Examples 1-4 as an electron transport layer.
  • Figure 8 is a single electron device characterization of the polymers (PNDIT-F6N, PNDIT-F3N) obtained in Examples 1 and 2.
  • Figure 9 is a UV-visible absorption spectrum of the polymer solution and film obtained in Example 5.
  • Example 10 is a JV graph of a positive-loading device of an organic-inorganic planar heterojunction perovskite solar cell (with CH 3 NH 3 PbI 3-x Cl x as a photoactive layer) using different electron transport layers in Example 7;
  • the practice of the present invention may employ conventional techniques of polymer chemistry within the skill of the art.
  • efforts are made to ensure the accuracy of the numbers used (including amounts, temperatures, reaction times, etc.), but some experimental errors and deviations should be considered.
  • the temperatures used in the following examples are expressed in ° C and the pressure is at or near atmospheric pressure. All solvents were purchased at analytical or chromatographic grades and all reactions were carried out under an inert atmosphere of argon. All reagents are commercially available unless otherwise indicated.
  • the solid was purified eluting eluted eluted eluted eluted elution g, monomer 2,6-(bis-5-bromo-2-thienyl)-N,N'-diisooctyl-1,4,5,8-naphthenediimide, yield 96 %.
  • 0.294 g was added to a 15 mL thick-walled pressure tube with a stir bar, 1 mL of a 20% aqueous solution of tetrabutylammonium hydroxide was added, and 2 mL of purified was added. Tetrahydrofuran and 4 mL of clean toluene, 25 mg of catalyst tetrakistriphenylphosphine palladium were added, nitrogen gas was passed for 20 minutes, sealed, heated to 110 ° C for 1 hour with stirring, and the reaction solution was poured into methanol to obtain a crude product, which was filtered, dried, and then polymer.
  • the anion exchange resin IRN-78 sold by Acros was first soaked in deionized water for 2 hours, then filled into a sand-filled column, and the polymer PNDIT-F6N-I 30 mg was dissolved in 10 mL of DMSO and added to the ion exchange resin column.
  • reaction (3) Add 4.0g (5mmol) of the product obtained in reaction (3) to a 100mL single-mouth bottle with magnetic stirrer, add 30mL of clean dichloromethane, stir, add excess diethylamine under nitrogen protection, avoid light at room temperature The reaction was continued for 36 hours. After the reaction was completed, it was directly concentrated, dried, and passed through a silica gel column to obtain a yellow solid, 1.4 g, yield 30%.
  • the polymer materials obtained in Examples 1-4 can be used as an electron transport layer in organic solar cell devices.
  • ITO conductive glass There are several ITO conductive glass, the sheet resistance is about 20 ohms/square, and the specification is 15 mm ⁇ 15 mm square.
  • the ITO glass sheets were treated with oxygen plasma for 4 minutes before use.
  • a PEDOT:PSS (polyethylenedioxythiophene) aqueous dispersion purchased from Bayer, Clevios P VP AI4083 was used as a hole transport layer, and a high speed spin coating (KW-4A) was applied to ITO at a high speed.
  • the thickness is determined by the solution concentration and the rotational speed, and is monitored by a surface profiler (Tritek Alpha-Tencor-500 type). After film formation, it was heated at 150 ° C for 20 minutes in the air and transferred to a glove box for use.
  • the active layer donor material conjugated polymer PTB7 and the acceptor material PC 71 BM were weighed in a clean bottle (mass ratio 1:1.5), and transferred to a nitrogen-protected film-forming glove box (VAC company) in chlorine.
  • a mixed solvent of benzene/1,8-diiodooctane (volume ratio: 100:3) was dissolved at a concentration of 11 mg/mL, and a film of 100 nm thick was formed on a PEDOT:PSS film.
  • the polymer materials obtained in the above Examples 1-4 were placed in a clean vial, transferred to a special glove box for nitrogen protection film formation, and a solution having a concentration of 0.5 mg/ml was prepared by using a polar solvent methanol, and placed on a stirring table to be stirred. Evenly.
  • the above solution was spin-coated on the active layer as an electron transport layer.
  • Aluminum (80 nm) was vacuum-deposited on the electron transport layer to form an electron collecting layer. All preparations were carried out in a nitrogen protected glove box.
  • the current-voltage characteristics of the device were measured by a Keithley 236 current-voltage-measurement system and a calibrated silicon photodiode.
  • the energy conversion efficiency of the device was measured under a standard solar spectrum AM 1.5G simulator (Oriel model 91192). The energy of the simulated sunlight was corrected to 100 mW/cm 2 using a standard silicon cell before testing. The relationship between current density and voltage of the device under illumination is shown in Figure 7. The specific device efficiency is shown in Table 1.
  • the decomposition temperatures of these several polymer materials are: 358 ° C, 216 ° C, 178 ° C, 332 ° C, 240 ° C, 178 ° C.
  • the LUMO energy levels of these polymer materials are very low, and the electron acceptor materials in the active layer have a matching energy level, and the reduction potential of the hydroxyl group-containing polymer is higher than that.
  • the reduction potentials of the two precursor polymers corresponding to them are low, which indicates that the hydroxyl group-containing polymer materials are less capable of being reduced than their respective two precursor polymers, and the corresponding LUMO energy levels are also lower. high.
  • the LUMO levels of these polymer materials were: -3.81 eV, -3.91 eV, -3.83 eV, -3.90 eV, -3.77 eV, -3.83 eV, respectively.
  • the polymer materials of the neutral amines connecting the different alkyl chains on the oxime differ in oxidation potential, and the oxy-oxide-containing polymers have higher oxidation potentials than their respective precursors.
  • the oxidation potential of the bulk polymer is low, which indicates that the hydroxyl-containing polymer materials are more oxidized than their respective two precursor polymers, and the corresponding HOMO energy levels are also higher.
  • PTB7 PC 71 BM active layer
  • JV graph showing the solar cell device obtained in Example 1-4 polymer prepared as an electron transport layer embodiment, the device-related properties as shown in Table 1.
  • Table 1 shows PTB7:PC 71 BM (mass ratio 1:1.5) as the active layer, and the polymer obtained in Examples 1-4 is the solar device performance of the electron transport layer.
  • the device structure is: ITO/PEDOT: PSS/PTB7: PC 71 BM/electron transport layer (5nm)/Al
  • Voc open circuit voltage
  • Jsc short circuit current
  • FF fill factor
  • PCE energy conversion efficiency
  • Table 2 shows the device properties of the polymers obtained in Examples 1 and 2 as single electron devices.
  • the n-type water-soluble conjugated polymer material containing a naphthalenedimide ring itself has a high electron mobility, indicating that it has a thick film processing in the processing process of the organic thin film battery device.
  • the possibility of an electron transport layer is not limited.
  • ITO conductive glass There are several ITO conductive glass, the sheet resistance is about 20 ohms/square, and the specification is 15 mm ⁇ 15 mm square.
  • the ITO glass sheets were treated with oxygen plasma for 4 minutes before use.
  • a PEDOT:PSS (polyethylenedioxythiophene) aqueous dispersion purchased from Bayer, Clevios P VP AI4083 was used as a hole transport layer, and a high speed spin coating (KW-4A) was applied to ITO at a high speed.
  • the thickness is determined by the solution concentration and the rotational speed, and is monitored by a surface profiler (Tritek Alpha-Tencor-500 type). After film formation, it was heated at 150 ° C for 20 minutes in the air and transferred to a glove box for use.
  • the CH 3 NH 3 I, PbI 2 and PbCl 2 (4:1:1 ratio) were blended and dissolved in 1 mL of DMF to prepare a 40% by mass solution, heated to 60 ° C, and stirred for 12 hours to obtain photoactivity.
  • the layer material precursor solution was spin-coated onto the PEDOT:PSS layer at 3000 rpm and then annealed at 100 ° C for 1 hour.
  • the electron transport layer is obtained by spin coating a layer of PNDIT-F6N on the surface of the photoactive layer, and the PNDIT-F6N in Example 1 is dissolved in a solvent such as chlorobenzene, dichlorobenzene, toluene, chloroform or xylene to prepare an electron transport layer solution.
  • the concentration ranges from 1 to 60 mg/ml.
  • the film thickness of PNDIT-F6N is usually 50 to 200 nm.
  • PC 61 BM dissolved in chlorobenzene, 30 mg/ml was used as an electron transport material in the comparative device. Finally, a silver electrode is evaporated by evaporation.
  • the comparison device uses PC 61 BM as the electron transport layer, and V oc and fill factor (FF) are significantly reduced.
  • the introduction of the electron transport layer material of the invention into the perovskite solar cell can significantly improve the carrier transport performance of the perovskite material, increase the open circuit voltage of the device, and significantly improve the photoelectric conversion performance of the device.

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Abstract

本发明属于光电器件技术领域，公开了一种电子传输层材料及其应用。该材料具有如下所示结构：(I) 其中n为1～10000的自然数，B为强极性基团，A1和A2为相同或者不同的芳环衍生物或者含有碳碳双键、碳氮键的共轭单元，M为A2与B之间的连接单元，M为具有1～20个碳原子的烷基，或烷基上一个或多个碳原子被氧原子、烯基、炔基、芳基或酯基中的一种以上官能团取代，氢原子被氟原子、氯原子、溴原子、碘原子或上述官能团取代。本发明将含强极性基团的共轭聚合物应用于电子传输层材料中，含强极性基团侧链的聚合物起明显的阴极界面修饰作用，提高载流子传输能力，获得了较好的器件性能。

Description

一种电子传输层材料及其应用 技术领域
本发明属于光电器件技术领域，特别涉及一种电子传输层材料及其应用。
背景技术
近些年来，由于能源消耗与日俱增，而煤石油天然气等传统能源储量有限，人们越来越重视以太阳能为代表的清洁能源的发展。有机光电材料与器件由于其材料易得，可低温溶剂加工，机械性能好，可大面积制备等特点，十分适合工业化生产和推广，具有十分广大的商业化前景。自1987年美国柯达公司邓青云研究组[Tang,C.W.；Van Slyke S.A.et al.；Applied Physics Letters,1987,51,913.]提出有机小分子薄膜电致发光器件和1990年英国剑桥大学R.H.Friend研究组[Burroughes J.H.,Bradley D.C.,Brown A.R.,et al.Nature,1990,347:539～541.]提出有机聚合物薄膜电致发光器件以来，有机平板显示技术取得巨大进展，目前已经步入产业化阶段，成为取代液晶显示器的下一代产品。与此同时，有机太阳电池、有机场效应晶体管、有机生物以及化学传感器等有机光电领域也取得蓬勃发展。现如今，经过科研工作者不断的努力，有机太阳电池的效率已突破12％(http://www.orgworld.de)，因此被业界所看好，市场化前景一片光明。
与此同时，基于溶液加工的有机-无机杂化钙钛矿类太阳电池最近在国际上倍受关注，该类钙钛矿材料具备吸收强，迁移率高，载流子寿命长，可调控带隙以及可采用多种方式加工等优点。2009年，Tsutomu Miyasaka研究组首次将钙钛矿结构的有机-无机杂化材料作为光活性层制备染料敏化太阳电池。其效率达到了3.81％(J.Am.Chem.Soc.2009,131,6050)。在短短几年内，实验室小面积器件的能量转换效率已经从3.81％提高到20％，成为最有潜力的太阳电池技术。
为了实现高效的有机薄膜电池器件，电子和空穴能否分别高效的被抽取到阴极和阳极是其中的关键。因此，很多高效的有机薄膜电池器件都是采用多层器件结构，即除了中间活性层外，还需要一层或多层的空穴传输层或电子传输 层。因此，除了开发优异的活性层材料，开发优异的电子传输层和空穴传输层也是实现高效有机薄膜电池器件的关键。
此前的研究发现共轭聚电解质及其中性前躯体是一类非常优异的电子传输层[Chem.Mater.2004,16,708；J.Am.Chem.Soc.2004,126,9845-9853；中国专利ZL200310117518.5]，这类共轭聚电解质材料不但可用于发光器件，还可作为界面修饰层可大幅度提高有机太阳电池、场效应晶体管及钙钛矿太阳电池的性能[Chem.Soc.Rev.2010,39,2500]。然而，这类共轭聚电解质材料的最低未占有轨道(LUMO)能级较高，且电子迁移率较低，使得这类材料在光电器件中的最优厚度只有5nm，对器件加工工艺的要求较为苛刻。
发明内容
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种电子传输层材料，极大的提高了太阳电池的开路电压及器件性能。
本发明再一目的在于提供上述电子传输层材料在光电器件中的应用。
本发明的目的通过下述方案实现：
一种电子传输层材料，具有如下结构：
Figure PCTCN2016075708-appb-000001
其中，n为1～10000的自然数，B为强极性基团，A1和A2为相同或者不同的芳环衍生物或者含有碳碳双键、碳氮键的共轭单元，M为A2与B之间的连接单元，M为具有1～20个碳原子的烷基，或烷基上一个或多个碳原子被氧原子、烯基、炔基、芳基或酯基中的一种以上官能团取代，氢原子被氟原子、氯原子、溴原子、碘原子或上述官能团取代。
所述强极性基团为胺基、季铵盐基团、磷酸根、磷酸酯基、磺酸根、羧基和羟基中的一种或两种以上。
所述的A1、A2为如下所示结构的一种或两种以上：
Figure PCTCN2016075708-appb-000002
其中n为1～10000的自然数，R为具有1～20个碳原子的烷基，或烷基上一个或多个碳原子被氧原子、烯基、炔基、芳基或酯基中的一种以上官能团取代，氢原子被氟原子、氯原子、溴原子、碘原子或上述官能团取代；
优选的，所述的A1为
Figure PCTCN2016075708-appb-000003
其中n为1～3的自然数，R为具有1～20个碳原子的烷基，或烷基上一个或多个碳原子被氧原子、烯基、炔基、芳基或酯基中的一种以上官能团取代，氢原子被氟原子、氯原子、溴原子、碘原子或上述官能团取代；所述的A2为如下所示结构的一种或两种以上：
Figure PCTCN2016075708-appb-000004
其中n为1～10000的自然数，R为具有1～20个碳原子的烷基，或烷基上一个或多个碳原子被氧原子、烯基、炔基、芳基或酯基中的一种以上官能团取代，氢原子被氟原子、氯原子、溴原子、碘原子或上述官能团取代；
当A1、A2为上述优选结构时，所述的电子传输层的材料可由以下方法制备得到：先将含有极性基团的A2单体和萘并酰亚胺环的单体等摩尔量混合，在有机碱和钯催化剂作用下得到极性基团未离子化的聚合物，接着将得到的聚合物在室温避光下进行盐化反应，得到极性基团离子化的聚合物，接着进一步将得到的离子化聚合物用含有不同对离子的离子交换树脂进行处理，再进行分离，即得到所述电子传输层材料。
上述电子传输层材料在光电器件中的应用。
本发明相对于现有技术，具有如下的优点及有益效果：
(1)本发明将含强极性基团的共轭聚合物应用于电子传输层材料中，含的强极性基团侧链的聚合物起到明显的阴极界面修饰作用，提高载流子传输能力，获得了较好的器件性能。
(2)含有萘并二酰亚胺环等吸电子基团的共轭聚合物材料具有和活性层中的电子受体材料相匹配的LUMO能级，因此更有利于电子由活性层中的受 体材料传输到电子传输层中。可以作为具有良好电荷传输能力的电子传输层应用在发光、光伏等光电器件中，改善器件的加工工艺和性能。
附图说明
图1为实施例1-4所得聚合物的傅立叶红外吸收图，其中，a图为聚合物PNDIT-F6N、PNDIT-F6N-I、PNDIT-F6N-OH的傅立叶红外吸收谱图；b图为聚合物PNDIT-F3N、PNDIT-F3N-I、PNDIT-F3N-OH的傅立叶红外吸收谱图。
图2为实施例1-4所得聚合物的热失重分析图。
图3为实施例1-4所得聚合物在甲醇溶液中的吸收光谱图。
图4为实施例1-4所得聚合物的薄膜吸收光谱图。
图5为实施例1-4所得聚合物的还原电势曲线比较图。
图6为实施例1-4所得聚合物的氧化电势曲线比较图。
图7为实施例1-4所得聚合物为电子传输层制备的有机太阳电池器件J-V曲线图。
图8为实施例1、2所得聚合物(PNDIT-F6N、PNDIT-F3N)单电子器件表征图。
图9为实施例5所得聚合物溶液和薄膜的紫外可见光吸收光谱。
图10为实施例7采用不同电子传输层的有机-无机平面异质结钙钛矿太阳电池(以CH3NH3PbI3-xClx为光活性层)正装器件的J-V曲线图；
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
本发明的实践可采用本领域技术内的聚合物化学的常规技术。在以下实施例中，努力确保所用数字(包括量、温度、反应时间等)的准确性，但应考虑一些实验误差和偏差。在以下实施例中所用的温度以℃表示，压力为大气压或接近大气压。所有溶剂为分析级或色谱级购买，并且所有反应在氩气惰性气氛下进行。除非另外指出，否则所有试剂都是商业获得的。
实施例1
聚{2,7-[9,9’-二(N,N-二乙基己基-6-胺基)芴]-共-5,5’-[2,6-(双-2-噻吩 基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺]}(PNDIT-F6N)的制备
化学反应流程如下所示，具体反应步骤和反应条件如下：
Figure PCTCN2016075708-appb-000005
(1)单体2,7-二(三亚甲基硼酸酯)-9,9’-二(N,N-二乙基己基-6-胺基)芴是按照文献(Adv.Mater.,2011,23,1665)公开方法制备。单体2,6-(双-5-溴-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺是按照文献(Chem.Mater.,2011,23, 4563)公开方法制备。具体步骤如下：取单体2,6-二溴-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺(按专利[PCT WO2011/144537A1]公开的方法制备)1.944g(3mmol)加入到带有搅拌子的100mL双口瓶中，通氮气10分钟后，取干净的甲苯40mL加入到反应瓶中，搅拌溶解，在氮气保护下，加入噻吩三丁基锡(按文献[Synthetic Metals 2006,156(2-4),166-175]公开的方法制备)2.5g(6.1mmol)，然后再加入催化剂四三苯基磷钯，搅拌加热至90℃，反应5小时。反应结束后倒入氯化铵的水溶液中，用二氯甲烷萃取，干燥，抽虑浓缩，所得固体用二氯甲烷石油醚(体积比1:1)为洗脱剂，硅胶过柱，得到的固体用甲醇-氯仿重结晶，得到红色纯品1.7g，产率86.7％。取上述步骤得到的产物1.308g(2mmol)加入到带有搅拌子的250mL双口瓶中，加入20mLDMF和60mL氯仿，搅拌溶解，然后取NBS 0.7832g溶于20mL氯仿和40mLDMF的混合溶剂中，于冰浴下缓慢滴加到反应瓶中，避光反应两天。反应结束后直接浓缩至固体，以固体用二氯甲烷石油醚(体积比1：1)为洗洗脱剂，硅胶过柱，得到的固体在用甲醇-氯仿重结晶，得到红色针状晶体1.6g，即单体2,6-(双-5-溴-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺，产率96％。
(2)将单体2,6-(双-5-溴-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺0.406g和单体2,7-二(三亚甲基硼酸酯)-9,9’-二(N,N-二乙基己基-6-胺基)芴0.364g加入到带有搅拌子的15mL厚壁耐压管，加入1mL20％的四丁基氢氧化胺水溶液，加入2mL纯化过的四氢呋喃和4mL干净甲苯，加入25mg催化剂四三苯基膦钯，通氮气20分钟，密封，搅拌加热至110℃反应1小时，将反应液沉到甲醇中得到粗品，过滤，干燥，然后将聚合物用丙酮在索氏提取器中洗涤24小时，然后再用氯仿反抽提出目标聚合物0.532g，产率89.7％。Mn＝17000，PDI＝1.6。
实施例2
聚{2,7-[9,9’-二(N,N-二甲基丙基-3-胺基)芴]-共-5,5’-[2,6-(双-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺]}(PNDIT-F3N)的制备
化学反应流程如下所示，具体反应步骤和反应条件如下：
Figure PCTCN2016075708-appb-000006
Figure PCTCN2016075708-appb-000007
将单体2,6-(双-5-溴-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺0.406g(制备方法同实施例1)和单体2,7-二(三亚甲基硼酸酯)-9,9’-二(N,N-二甲基丙基-3-胺基)芴(按照文献[J.Am.Chem.Soc.2004,126,9845-9853]公开的方法制备)0.294g加入到带有搅拌子的15mL厚壁耐压管，加入1mL20％的四丁基氢氧化胺水溶液，加入2mL纯化过的四氢呋喃和4mL干净甲苯，加入25mg催化剂四三苯基膦钯，通氮气20分钟，密封，搅拌加热至110℃反应1小时，将反应液沉到甲醇中得到粗品，过滤，干燥，然后将聚合物用丙酮在索氏提取器中洗涤24小时，然后再用氯仿反抽提出目标聚合物0.497g，产率94.3％。Mn＝25000,PDI＝1.4。
实施例3
聚{2,7-[9,9’-二(N,N-二乙基己基-6-氢氧化胺)芴]-共-5,5’-[2,6-(双-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺]}(PNDIT-F6N-OH)的制备
化学反应流程如下所示，具体反应步骤和反应条件如下：
Figure PCTCN2016075708-appb-000008
取实施例1制备得到的PNDIT-F6N 50mg于50mL单口瓶中，加入10mL干净氯仿，搅拌溶解，然后往反应液中加入0.5mL碘甲烷，密封，避光，于室温下反应48小时，反应过程中，若有固体析出，则往反应液中加入DMSO至溶解。反应结束后，浓缩，于乙酸乙酯中沉出固体，固体再溶解，再沉出，过滤，干燥后得到产物聚{2,7-[9,9’-二(N,N-二乙基己基-6-碘化胺)芴]-共-5,5’-[2,6-(双-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺]}(PNDIT-F6N-I)；
先将Acros公司出售的阴离子交换树脂IRN-78用去离子水浸泡2小时，然后填充到具砂板填充柱中，取聚合物PNDIT-F6N-I 30mg用10mL DMSO溶解，加入到离子交换树脂柱中，用DMSO水(体积比1：1)混合溶剂过柱，将过柱后得到的溶液浓缩，于乙酸乙酯中沉出，干燥得到产物聚{2,7-[9,9’-二(N,N-二乙基己基-6-氢氧化胺)芴]-共-5,5’-[2,6-(双-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺]}(PNDIT-F6N-OH)。
实施例4
聚{2,7-[9,9’-二(N,N-二甲基丙基-3-氢氧化胺)芴]-共-5,5’-[2,6-(双-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺]}(PNDIT-F3N-OH)的制备
化学反应流程如下所示，具体反应步骤和反应条件如下：
Figure PCTCN2016075708-appb-000009
具体实施方法同实施例3，将原料由实施例1制备得到的PNDIT-F6N替换为实施例2中制备得到的PNDIT-F3N。
实施例5
聚{2,5-噻吩-共-N,N’-(4-[6-(二乙基胺基)己氧基]苄基)-1,4,5,8-萘并二酰亚胺]}(PNDIPNT)的制备
化学反应流程如下所示，具体反应步骤和反应条件如下：
Figure PCTCN2016075708-appb-000010
(1)单体N-叔丁酯基-4-羟基苄胺的制备
取单体对羟基苄胺12.3g(100mmol)加入到带有搅拌子的100mL双口瓶中，通氮气10分钟后，取干净的甲醇40mL加入到反应瓶中，搅拌溶解，在氮气保护下，将反应瓶置于冰浴下冷却至溶液温度为4℃，取二碳酸二叔丁酯26.2g(120mmol)缓慢滴加到反应液中，在冰浴下继续反应2小时，反应结束后，浓缩，减压蒸馏得到产物18.3g，产率83％。
(2)单体4-(6-溴己氧基)苄胺的制备
取反应(1)得到的产物13.4g(90mmol)加入到带有磁力搅拌子的500mL三口瓶中，通氮气10分钟，加入二溴己烷100mL，加入2mol/L的KOH水溶液50mL，加入溴化四丁基铵1g，加热至回流反应6小时。反应结束后，倒入水中，萃取分离，得到有机相，减压蒸馏除去过量二溴己烷，得到粗产物，不提纯直接将过量的三氟乙酸加入到含粗产物的二氯甲烷溶液中反应，室温下反应3小时，浓缩后得到油状液体溶于甲醇溶液，用4mol/L的氢氧化钠溶液中和至碱性，用二氯甲烷萃取得到有机相，无水硫酸镁干燥，过滤，浓缩得到粗产物，减压蒸馏得到产物20.0g，产率78％。
(3)单体2,6-二溴-N,N’-二[4-(6-溴己氧基)苄基]-1,4,5,8-萘并二酰亚胺的 制备
具体实施方法参考[PCT WO2011/144537 A1]公开的方法制备。
(4)单体2,6-二溴-N,N’-二[4-(6-二乙胺基)己氧基)苄基]-1,4,5,8-萘并二酰亚胺的制备
取反应(3)得到的产物4.0g(5mmol)加入到带有磁力搅拌子的100mL单口瓶中，加入干净二氯甲烷30mL，搅拌，在氮气保护下，加入过量二乙胺，室温下避光反应36小时。反应结束后，直接浓缩，烘干，过硅胶柱后得到黄色固体1.4g，产率30％。
(5)聚{2,5-噻吩-共-N,N’-(4-[6-(二乙基胺基)己氧基]苄基)-1,4,5,8-萘并二酰亚胺]}(PNDIPNT)的制备
取步骤(4)得到的产物236.4mg(0.25mmol)，2,5-二三甲基锡噻吩102.4mg(0.25mmol)，加入到25mL带有磁力搅拌子的两口圆底烧瓶中，氮气抽换气3次，取氯苯10mL注射到反应瓶中搅拌，在通氮气的条件下，加入催化剂Pd2(dba)34mg，加入配体P-(toyl)38mg，加热至95℃反应48小时。反应结束后将反应液沉到甲醇中得到粗品，过滤，干燥，然后将聚合物先后用丙酮，正己烷和二氯甲烷抽提洗涤24小时，然后再用氯仿反抽提出目标聚合物201.8mg，产率87％。Mn＝34000,PDI＝1.6。
实施例6
以实施例1-4所得聚合物材料为例说明此类聚合物材料能作为电子传输层在有机太阳电池器件中应用
ITO导电玻璃若干，方块电阻约20欧/方，规格为15毫米×15毫米方片。依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清洗半小时以上，置于恒温烘箱备用。使用前，ITO玻璃片在氧等离子体处理4分钟。将PEDOT:PSS(聚乙烯二氧基噻吩)水分散液(购自Bayer公司，Clevios P VP AI4083)作为空穴传输层，采用匀胶机(KW-4A)高速旋涂于ITO上，膜厚40纳米左右为佳，厚度由溶液浓度和转速决定，用表面轮廓仪(Tritek公司Alpha-Tencor-500型)实测监控。成膜后，于空气中150度加热20分钟，转移至手套箱备用。
将活性层给体材料共轭聚合物PTB7和受体材料PC71BM于干净瓶中称量后(质量比为1:1.5)，转入氮气保护成膜专用手套箱(VAC公司)，在氯苯/1,8-二碘辛烷的混合溶剂(体积比100:3)中溶解，浓度为11mg/mL，在PEDOT:PSS 膜上甩100nm厚的膜。将上述实施例1-4所得聚合物材料置于洁净小瓶中，转入氮气保护成膜专用手套箱中，用极性溶剂甲醇配成浓度为0.5mg/ml的溶液，置于搅拌台上搅拌均匀。将上述溶液在活性层上旋涂为电子传输层。在电子传输层上真空蒸镀铝(80nm)为电子收集层。所有制备过程均在氮气保护手套箱中进行。器件的电流-电压特性，由Keithley236电流电压-测量系统及一个经校正的硅光二极管中测得。器件的能量转换效率在标准太阳光谱AM1.5G模拟器(Oriel model 91192)下测得。模拟太阳光的能量在测试前用标准硅电池校正为100mW/cm2。器件在光照下的电流密度与电压关系如图7所示，具体器件效率如表1所示。
由图1中可以看出，季铵化前后红外吸收光谱图差别不大，但通过离子交换后，将碘离子交换为氢氧根离子，在红外谱图上明显多了一个氢氧根的红外吸收峰。
由图2可以看出，这几个聚合物材料的分解温度分别为：358℃、216℃、178℃、332℃、240℃、178℃。
从图3、4中可以明显看出含氢氧根的聚合物的吸收光谱和它们本身对应的两个前驱体聚合物材料的吸收光谱差很多，表现出共轭主链被n-型掺杂的现象，这说明本发明中所举实施例材料可以通过在胺基上引入不同对离子而实现对聚合物材料吸收光谱的改变。
由图5可以看出，这几个聚合物材料的LUMO能级都很低，和活性层中的电子受体材料有较匹配的能级，其中含氢氧根的聚合物的还原电位要比它们本身对应的两个前驱体聚合物的还原电位低，这说明含氢氧根的聚合物材料被还原的能力要比它们本身对应的两个前驱体聚合物差，对应的LUMO能级也较高。这几个聚合物材料的LUMO能级分别为：-3.81eV、-3.91eV、-3.83eV、-3.90eV、-3.97eV、-3.83eV。
从图6中可以看出，芴上连接不同烷基链的中性胺的聚合物材料在氧化电位上有差别，此外含氢氧根的聚合物的氧化电位要比它们本身对应的两个前驱体聚合物的氧化电位低，这说明含氢氧根的聚合物材料被氧化的能力要比它们本身对应的两个前驱体聚合物强，对应的HOMO能级也较高。
图7为以PTB7:PC71BM为活性层，实施例1-4所得聚合物作为电子传输层制备的太阳能电池器件的J-V曲线图，相关器件性能如表1所示。
表1以PTB7:PC71BM(质量比1:1.5)为活性层,实施例1-4所得聚合物为电子传输层的太阳能器件性能。
器件结构为：ITO/PEDOT:PSS/PTB7:PC71BM/电子传输层(5nm)/Al
表1
电子传输层 Voc(V) Jsc(mA/cm2) FF(％) PCE(％)
PNDIT-F3N 0.74 15.63 72.87 8.4
PNDIT-F6N 0.74 15.39 73.03 8.3
PNDIT-F3N-I 0.74 15.34 72.78 8.3
PNDIT-F6N-I 0.74 15.59 73.12 8.4
PNDIT-F3N-OH 0.73 15.05 73.65 8.1
PNDIT-F6N-OH 0.74 14.96 73.85 8.2
其中Voc为：开路电压，Jsc为：短路电流，FF为：填充因子，PCE为：能量转化效率。
从中可以看出以含萘并二酰亚胺环的n-型水醇溶共轭聚合物材料为电子传输层的器件都表现出优异的器件性能，表明这类材料都具有优异的界面修饰性能。
图8为实施例1、2所得聚合物PNDIT-F6N、PNDIT-F3N的单电子器件表征图，相关器件性能如表2所示。
表2为实施例1、2所得聚合物做成单电子器件的器件性能。
器件结构为：ITO/Al/聚合物(100nm)/Al
表2
聚合物 电子迁移率
PNDIT-F3N 1.9x10-4cm2V-1s-1
PNDIT-F6N 1.1x10-4cm2V-1s-1
从中可以看出含萘并二酰亚胺环的n-型水醇溶共轭聚合物材料本身具有较高的电子迁移率，表明其具有成为在有机薄膜电池器件加工工艺中可厚膜加工的电子传输层的可能性。
从图9可以看出聚合物PNDIPNT的薄膜吸收光谱要明显比溶液的红移，其中分子内电荷转移吸收峰的红移更为明显由原来的542nm红移到607nm，表明在薄膜状态下，聚合物有很好的堆积，有利于电子的传输。
实施例7
有机-无机平面异质结钙钛矿太阳电池的制备：
ITO导电玻璃若干，方块电阻约20欧/方，规格为15毫米×15毫米方片。依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清洗半小时以上，置于恒温烘箱备用。使用前，ITO玻璃片在氧等离子体处理4分钟。将PEDOT:PSS(聚乙烯二氧基噻吩)水分散液(购自Bayer公司，Clevios P VP AI4083)作为空穴传输层，采用匀胶机(KW-4A)高速旋涂于ITO上，膜厚40纳米左右为佳，厚度由溶液浓度和转速决定，用表面轮廓仪(Tritek公司Alpha-Tencor-500型)实测监控。成膜后，于空气中150度加热20分钟，转移至手套箱备用。
取CH3NH3I、PbI2和PbCl2(比例为4:1:1)共混溶于1mL DMF中，配成质量分数为40％的溶液，加热至60℃，搅拌12小时得到光活性层材料前驱体溶液，在3000 rpm的转速下将其旋涂到PEDOT:PSS层上，然后100℃加热退火1小时。电子传输层通过在光活性层表面旋涂一层PNDIT-F6N溶液得到，将实施例1中的PNDIT-F6N溶于氯苯、二氯苯、甲苯、氯仿、二甲苯等溶剂配制电子传输层溶液，浓度范围为1～60毫克/毫升。PNDIT-F6N膜厚通常采用50～200纳米。同时，在对比器件中采用PC61BM(溶于氯苯，30毫克/毫升)作为电子传输材料。最后采用蒸镀的方法蒸镀一层银电极。
从图10中可以看出，在器件结构为正装：ITO/PEDOT/Perovskite/PNDIT-F6N/Ag下效率最高的器件的短路电流(Jsc)和开路电压(Voc)分别为22.8mA/cm2和0.93V。而对比器件采用PC61BM作为电子传输层，Voc及填充因子(FF)明显减低。
具体太阳电池器件效率如表3所示。
从表3中可以看出，将通常所用的电子传输层PC61BM替换为新材料PNDIT-F6N,Voc、Jsc及FF均有明显提高，器件效率由10.1％提高至约14％，这说明整个器件内载流子传输更平衡。特别的，由于PNDIT-F6N材料含有强极性基团，在与金属接触时，可减低金属功函，起到明显的界面修饰作用，提高开路电压。
表3 器件结构：ITO/PEDOT/Perovskite/ETL/Ag
阴极界面层 Voc(V) Jsc(mA/cm2) FF(％) PCE(％)
PC61BM 0.88 20.1 57.1 10.1
PNDIT-F6N 0.93 22.7 64.0 14.0
由此可见，本发明的电子传输层材料引入钙钛矿太阳电池，可以显著的改善钙钛矿材料的载流子传输性能，提高器件的开路电压，并显著提高器件的光电转换性能。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (6)

  1. 一种电子传输层材料，其特征在于具有如下结构：
    Figure PCTCN2016075708-appb-100001
    其中，n为1～10000的自然数，B为强极性基团，A1和A2为相同或者不同的芳环衍生物或者含有碳碳双键、碳氮键的共轭单元，M为A2与B之间的连接单元，M为具有1～20个碳原子的烷基，或烷基上一个或多个碳原子被氧原子、烯基、炔基、芳基或酯基中的一种以上官能团取代，氢原子被氟原子、氯原子、溴原子、碘原子或上述官能团取代。
  2. 根据权利要求1所述的电子传输层材料，其特征在于：所述强极性基团为胺基、季铵盐基团、磷酸根、磷酸酯基、磺酸根、羧基和羟基中的一种或两种以上。
  3. 根据权利要求1或2所述的电子传输层材料，其特征在于：所述的A1、A2为如下所示结构的一种或两种以上：
    Figure PCTCN2016075708-appb-100002
    其中n为1～10000的自然数，R为具有1～20个碳原子的烷基，或烷基上一个或多个碳原子被氧原子、烯基、炔基、芳基或酯基中的一种以上官能团取代，氢原子被氟原子、氯原子、溴原子、碘原子或上述官能团取代。
  4. 根据权利要求1或2所述的电子传输层材料，其特征在于：
    所述的A1为
    Figure PCTCN2016075708-appb-100003
    其中n为1～3的自然数，R为具有1～20个碳原子的烷基，或烷基上一个或多个碳原子被氧原子、烯基、炔基、芳基或酯基中的一种以上官能团取代，氢原子被氟原子、氯原子、溴原子、碘原子或上述官能团取代；
    所述的A2为如下所示结构的一种或两种以上：
    Figure PCTCN2016075708-appb-100004
    其中n为1～10000的自然数，R为具有1～20个碳原子的烷基，或烷基上一个或多个碳原子被氧原子、烯基、炔基、芳基或酯基中的一种以上官能团取代，氢原子被氟原子、氯原子、溴原子、碘原子或上述官能团取代。
  5. 一种根据权利要求4所述的电子传输层材料的制备方法，其特征在于包括以下步骤：先将含有极性基团的A2单体和萘并酰亚胺环的单体等摩尔量混合，在有机碱和钯催化剂作用下得到极性基团未离子化的聚合物，接着将得到的聚合物在室温避光下进行盐化反应，得到极性基团离子化的聚合物，接着进一步将得到的离子化聚合物用含有不同对离子的离子交换树脂进行处理，再进行分离，即得到所述聚合物材料。
  6. 根据权利要求1～4任一项所述的电子传输层材料在光电器件中的应用。
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