CN110862518A - 基于多元稠环结构的多元共聚物及其在有机光电器件中的应用 - Google Patents

基于多元稠环结构的多元共聚物及其在有机光电器件中的应用 Download PDF

Info

Publication number
CN110862518A
CN110862518A CN201910979951.0A CN201910979951A CN110862518A CN 110862518 A CN110862518 A CN 110862518A CN 201910979951 A CN201910979951 A CN 201910979951A CN 110862518 A CN110862518 A CN 110862518A
Authority
CN
China
Prior art keywords
groups
branched
substituted
cyclic alkyl
alkyl chain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910979951.0A
Other languages
English (en)
Other versions
CN110862518B (zh
Inventor
黄飞
张佳滨
贾涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201910979951.0A priority Critical patent/CN110862518B/zh
Publication of CN110862518A publication Critical patent/CN110862518A/zh
Application granted granted Critical
Publication of CN110862518B publication Critical patent/CN110862518B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/122—Copolymers statistical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1412—Saturated aliphatic units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/143—Side-chains containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/411—Suzuki reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/414—Stille reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Photovoltaic Devices (AREA)

Abstract

本发明涉及基于多元稠环结构的多元共聚物及其在有机光电器件中的应用。所述共聚物的主链含有多元稠环受体‑给体‑受体型结构单元。通过多元共聚单体种类及共聚比例的控制，可以对材料的光电性能进行调控，获得的多元共聚物具有更宽的光谱吸收与更高的摩尔吸收系数。该类型聚合物可以作为电子受体，应用于有机光电器件中，获得较高的器件光电转换效率。

Description

基于多元稠环结构的多元共聚物及其在有机光电器件中的 应用
技术领域
本发明涉及高分子光电材料领域，具体涉及一类基于多元稠环结构的多元共聚物及其在有机光电器件中的应用。
背景技术
能源短缺、环境污染是我国经济可持续发展面临的重大问题。发展新型绿色能源技术是解决上述问题的重要途径之一，而太阳能发电(光伏发电)是众多绿色、可再生能源中的佼佼者，对于降低污染和减少二氧化碳排放，实现低碳经济的发展具有重要意义。有机/聚合物太阳电池具有成本低廉、可采用溶液加工制备大面积器件、以及可制成柔性器件等突出优点，且可与无机半导体太阳电池的应用领域很好的互补，具有巨大的商业开发价值和应用前景。
近几年来，基于富勒烯受体PCBM的聚合物太阳能电池受到科学家们的广泛研究和关注，单节太阳能电池的转化效率突破11％。但是富勒烯衍生物本身所具有的不稳定性以及高成本，使得科学家开始寻找能代替它们的受体材料，以适应实际生产的应用。作为聚合物太阳电池领域的一个重要分支，全聚合物太阳能电池是一类使用n-型聚合物取代富勒烯衍生物或者非富勒烯共轭小分子作为受体的新型太阳电池技术。聚合物受体材料取代富勒烯受体，可以克服富勒烯受体存在的可见光区吸光弱、能级调控范围窄、光化学不稳定、形貌稳定性差等缺点。此外，全聚合物太阳电池还具有更好的成膜与加工性能，光伏器件也具有更好的机械性能，有利于柔性有机太阳电池的大面积集成化制备。因此，近年来，全聚合物太阳电池不断受到研究者的关注。
尽管全聚合物太阳电池具有很多优势和发展潜能，但目前全聚合物太阳电池的效率仍低于富勒烯以及非富勒烯小分子受体型太阳电池。其主要原因是现有体系的聚合物受体存在光谱吸收范围窄、摩尔吸收系数低等缺点。通过主链上引入多元稠环结构制备多元共聚物，通过分子结构剪裁获得高摩尔吸光系数、宽光谱吸收且能级化学可调的聚合物，有望解决上述问题，提升以聚合物为电子受体的有机太阳电池的性能。
发明内容
本发明的目的在于设计并合成基于多元稠环结构的多元共聚物用于有机光电器件中。
本发明所提供的一类基于多元稠环结构的多元共聚物，其结构如式I所示：
Figure BDA0002234856880000021
其中，x、y、z为1～10000的自然数；A为基于多元稠环的受体-给体-受体型结构单元；B为缺电性单元；C为共轭芳环单元；A具有如下结构的一种或多种：
Figure BDA0002234856880000022
其中，R1、R2为氢原子、卤素原子；或者R1、R2为选自C1～C60的直链、支链或者环状烷基链，其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；或者所述直链、支链或者环状烷基链中的氢原子被氟原子或上述官能团取代。
进一步地，B为缺电性结构单元，具有如下结构的一种或多种：
Figure BDA0002234856880000031
其中，R3为氢原子、卤素原子；或者R3为选自C1～C60的直链、支链或者环状烷基链，其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；或者所述直链、支链或者环状烷基链中的氢原子被氟原子或上述官能团取代。
进一步地，C为共轭芳环单元，选自如下结构的任一种或多种：
Figure BDA0002234856880000041
其中，R4为氢原子、卤素原子；或者R4为选自C1～C60的直链、支链或者环状烷基链，其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；或者所述直链、支链或者环状烷基链中的氢原子被氟原子或上述官能团取代。
基于多元稠环结构的多元共聚物用于有机光电器件中。
本发明所述基于多元稠环结构的多元共聚物通过Suzuki或Stille偶联聚合反应得到。
与现有技术相比，本发明具有以下优点：
(1)本发明将基于多元稠环的受体-给体-受体型结构单元引入多元共聚物中，能够扩宽聚合物的光谱吸收范围，增强聚合物的光谱吸收强度，实现太阳光的有效吸收和利用；
(2)通过调控聚合单元的种类与比例，能够有效调控多元共聚物的光谱吸收、能级结构等特性，经过结构筛选优化获得的多元共聚物作为电子受体应用于有机太阳电池，能够获得优异的器件性能。
附图说明
图1为实施例所述共聚物PJ10、PJ20及参比均聚物N2200的结构式；
图2为所述代表性多元共聚物PJ10、PJ20与参比均聚物N2200在氯仿溶液中的紫外-可见光-近红外吸收谱图；
图3为所述代表性多元共聚物PJ10、PJ20与参比均聚物N2200薄膜状态下归一化的紫外-可见光-近红外吸收谱图；
图4为所述代表性共聚物PJ10、PJ20与参比均聚物N2200的循环伏安曲线；
图5为所述代表性多元共聚物PJ10、PJ20与参比均聚物N2200作为电子受体与给体聚合物PBDB-T匹配制备的太阳电池器件的电流-电压曲线图。
具体实施方式
下面通过具体实施例对本发明作进一步的说明，其目的在于帮助更好的理解本发明的内容，具体包括合成、表征与器件制备，但这些具体实施方案不以任何方式限制本发明的保护范围。
实施例1：化合物TTPBT-CHO按照[Joule 2019,3(4),1140-1151]公开的方法合成。
实施例2：聚合单体M1的合成
在两口圆底烧瓶中加入双醛化合物TTPBT-CHO(738mg,0.5mmol),化合物IC-Br(683mg,2.5mmol)，抽换气三次并使体系填充氮气。用注射器在反应瓶中加入氯仿(80mL)与吡啶(2mL)，反应液在80℃温度下搅拌反应18小时。待反应液冷却至室温，粗产物经硅胶柱层析提纯，洗脱剂是石油醚/二氯甲烷(2:1)，得黑色固体化合物M1(874mg，88％)。1H NMR(500MHz,CDCl3):δ9.13(s,2H),8.84(s,1H),8.52(d,J＝8.4Hz,1H),8.03(d,J＝1.6Hz,1H),7.89–7.78(m,3H),4.77(m,4H),3.20(t,J＝7.5Hz,4H),2.16(m,2H),1.91–1.83(m,4H),1.55-1.49(m,4H),1.38-1.36(m,4H),1.33-1.23(m,28H),1.24-1.12(m,36H),1.04-0.99(m,36H),0.88-0.81(m,22H).13C NMR(126MHz,CDCl3):δ187.32,186.91,159.83,159.21,153.59,147.46,145.13,141.35,138.49,138.29,137.78,137.60,137.17 136.01,135.42,134.15,134.12,134.09,133.49,130.80 130.77,130.74,130.71,130.14,129.46,128.15,126.70,126.34,124.50,120.13,115.26,115.11,114.90,114.55,113.60,113.56,68.80,68.28,55.70,39,13,31.97,31.95,31.93,31.23,30.54,29.90,29.82,29.79,29.74,29.71,29.69,29.65,29.57,29.49,29.46,29.42,29.37,25.59,22.72,22.70,14.14.MS(MALDI-TOF):m/z 1986.5157(M+).
Figure BDA0002234856880000061
实施例3：所述代表性聚合物PJ10的合成：
在25mL干燥的双口瓶中加入聚合单体M1(59.6mg，0.03mmol)、M2(266mg，0.27mmol)与M3(147.6mg，0.3mmol)，催化剂三(二亚苄基茚丙酮)二钯(5.4mg)，配体三邻甲基苯基膦(8.1mg)，通过真空双排管进行抽换气三次，用注射器加入溶剂氯苯(6mL)。反应液在140℃温度下搅拌反应48小时。恢复至室温后，将聚合物溶液滴加到300mL的甲醇中，过滤得到聚合物沉淀。聚合物通过索氏抽提装置先后以甲醇、正己烷、二氯甲烷、氯仿抽提，收集氯仿相浓缩后在甲醇中沉淀，过滤收集并烘干得黑色目标聚合物PJ10(269mg，82％)。GPC:Mn＝56.26kDa,Mw＝120.15kDa.1H NMR(600MHz,C2D2Cl4,120℃):δ9.21(s,0.2H),8.87-8.85(m,2H),8.77(d,0.1H),4.83(m,0.4H),4.17(m,4H),3.30(m,0.4H),2.16(m,0.2H),2.08-2.06(m,2H),2.00(m,0.4H),1.46-1.07(m,72H),0.99-0.85(m,13H)。通过聚合物核磁中M1所属特征峰δ9.21,8.77,4.83,3.30,2.16,2.00等化学位移的积分确定单体M1在聚合物主链的比例约为10％，与聚合单体投料比相符。
Figure BDA0002234856880000071
实施例4：代表性聚合物PJ20的合成：
在25mL干燥的双口瓶中加入聚合单体M1(119.2mg，0.06mmol)、M2(236.4mg，0.24mmol)与M3(147.6mg，0.3mmol)，催化剂三(二亚苄基茚丙酮)二钯(5.4mg)，配体三邻甲基苯基膦(8.1mg)，通过真空双排管进行抽换气三次，用注射器加入溶剂氯苯(6mL)。反应液在140℃温度下搅拌反应48小时。恢复至室温后，将聚合物溶液滴加到300mL的甲醇中，过滤得到聚合物沉淀。聚合物通过索氏抽提装置先后以甲醇、正己烷、二氯甲烷、氯仿抽提，收集氯仿相浓缩后在甲醇中沉淀，过滤收集并烘干得黑色目标聚合物PJ20(308mg，86％)。GPC:Mn＝39.61kDa,Mw＝67.86kDa.1H NMR(600MHz,C2D2Cl4,120℃)δ9.21(s,0.4H),8.87-8.85(m,2H),8.77(d,0.2H),4.83(m,0.8H),4.17(m,4H),3.30(m,0.4H),2.16(m,0.4H),2.08-2.06(m,2H),2.00(m,0.8H),1.46-1.07(m,75H),0.99-0.85(m,14H)。通过聚合物核磁中M1所属特征峰δ9.21,8.77,4.83,3.30,2.16,2.00等化学位移的积分确定单体M1在聚合物主链的比例约为20％，与聚合单体投料比相符。
Figure BDA0002234856880000081
实施例5:
以实施例1～4合成的代表性聚合物PJ10、PJ20及参比均聚物N2200作为电子受体用于有机太阳电池器件中(ITO阳极/阳极界面层/活性层/阴机界面层/阴极)
将购买到的氧化铟锡(ITO)玻璃分别依次用丙酮超声清洗10分钟；低浓度micro级洗涤剂超声清洗15分钟；超纯去离子水超声清洗2～3次，每次10分钟；色谱纯异丙醇超声清洗10～15分钟，经过清洗的ITO玻璃基片用氧气等离子处理5分钟待用。在ITO基片上旋涂一层聚乙撑二氧噻吩：聚苯乙烯磺酸盐(PEDOT:PSS)，150℃干燥15min，将实施例1～4得到的聚合物PJ10、PJ20以及参比均聚物N2200与给体PBDB-T共混配成氯苯溶液，旋涂在PEDOT:PSS阳极界面层上作为活性层，在活性层上旋涂一层PFN-Br作为阴极界面层，在界面层上蒸镀厚度约80nm的Ag作为阴极。电池有效面积通过掩模版控制，为0.04cm2。所有制备过程均在氮气氛围的手套箱内进行。器件性能测试在Oriel91192型AM 1.5G太阳光模拟灯的照射下进行，辐射度为1kW/m2，使用Keithley 2400型数字源表测试J-V曲线。所制备的正装电池器件的电流-电压曲线如图5所示，相关的数据在表一中列出。可以看出，本发明设计的多元共聚物作为电子受体材料用于活性层能够极大地同步提升电池器件的短路电流与填充因子，获得更好的电池器件性能。
表1为基于所述聚合物PJ10、PJ20与参比均聚物N2200作为电子受体制备的有机太阳电池的器件性能参数
器件结构：ITO/PEDOT:PSS/PBDB-T:Acceptor/PFN-Br/Ag
Figure BDA0002234856880000091
图2为所述代表性多元共聚物PJ10、PJ20与参比均聚物N2200在氯仿溶液中的紫外-可见光-近红外吸收谱图；由图可见，所述多元共聚物相较于均聚物N2200，在长波区的吸收强度提高，吸收范围扩宽，摩尔吸光系数由均聚物N2200的2.38*104cm-1提升至PJ20的5.78*104cm-1；图3为所述代表性多元共聚物PJ10、PJ20与参比均聚物N2200薄膜状态下归一化的紫外-可见光-近红外吸收谱图；由图可见，所述共聚物PJ10与PJ20在778nm处出现尖峰，为共聚单体M1所属特征峰；图4为所述代表性共聚物PJ10、PJ20与参比均聚物N2200的循环伏安曲线；Ag/AgCl电极通过Fc/Fc+校正为0.38V，通过电化学测得的N2200、PJ10与PJ20的氧化电位分别为1.49V，1.46V与1.44V，计算得对应的HOMO能级分别为-5.91eV，-5.88eV与-5.86eV；电化学测得的N2200、PJ10与PJ20的还原电位分别为-0.50V，-0.47V与-0.46V，计算得对应LUMO能级分别-3.92eV，-3.95eV与-3.96eV。

Claims (5)

1.基于多元稠环结构的多元共聚物，其特征在于，具有以下结构：
Figure FDA0002234856870000011
其中，x、y、z为1～10000的自然数；A为基于多元稠环的受体-给体-受体型结构单元；B为缺电性单元；C为共轭芳环单元。
2.根据权利要求1所述基于多元稠环结构的多元共聚物，其特征在于，A具有如下结构的一种以上：
Figure FDA0002234856870000012
所述的R1、R2为氢原子、卤素原子；或者R1、R2为选自C1～C60的直链、支链或者环状烷基链，其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；或者所述直链、支链或者环状烷基链中的氢原子被氟原子或上述官能团取代。
3.根据权利要求1所述基于多元稠环结构的多元共聚物，其特征在于，B为缺电性单元，选自如下结构的一种以上：
Figure FDA0002234856870000021
其中，结构式中的R3为氢原子、卤素原子；或者R3为选自C1～C60的直链、支链或者环状烷基链，其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；或者所述直链、支链或者环状烷基链中氢原子被氟原子或上述官能团取代。
4.根据权利要求1所述基于多元稠环结构的多元共聚物，其特征在于，C为共轭芳环单元，选自如下结构的任一种以上：
Figure FDA0002234856870000031
其中，R4为氢原子、卤素原子，或者R4为选自C1～C60的直链、支链或者环状烷基链，其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；或者所述直链、支链或者环状烷基链中氢原子被氟原子或上述官能团取代。
5.根据权利要求1～4任一项所述基于多元稠环结构的多元共聚物用于有机光电器件中。
CN201910979951.0A 2019-10-15 2019-10-15 基于多元稠环结构的多元共聚物及其在有机光电器件中的应用 Active CN110862518B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910979951.0A CN110862518B (zh) 2019-10-15 2019-10-15 基于多元稠环结构的多元共聚物及其在有机光电器件中的应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910979951.0A CN110862518B (zh) 2019-10-15 2019-10-15 基于多元稠环结构的多元共聚物及其在有机光电器件中的应用

Publications (2)

Publication Number Publication Date
CN110862518A true CN110862518A (zh) 2020-03-06
CN110862518B CN110862518B (zh) 2021-05-14

Family

ID=69652518

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910979951.0A Active CN110862518B (zh) 2019-10-15 2019-10-15 基于多元稠环结构的多元共聚物及其在有机光电器件中的应用

Country Status (1)

Country Link
CN (1) CN110862518B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112552489A (zh) * 2020-11-09 2021-03-26 山东师范大学 一种非对称非富勒烯化合物及其制备方法与应用
CN115386069A (zh) * 2022-09-29 2022-11-25 位速科技股份有限公司 共聚物、有源层及有机光伏元件

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103848967A (zh) * 2012-11-28 2014-06-11 海洋王照明科技股份有限公司 一种含噻吩并噻吩、苯并噻二唑和环戊并二噻吩聚合物及其制备与应用
CN104169347A (zh) * 2012-03-16 2014-11-26 默克专利股份有限公司 共轭聚合物
CN104211912A (zh) * 2013-05-29 2014-12-17 海洋王照明科技股份有限公司 共轭聚合物及其制备方法与应用
CN104557968A (zh) * 2013-10-29 2015-04-29 中国科学院化学研究所 基于二噻吩并引达省的a-d-a共轭分子及其制备方法和应用
CN105315298A (zh) * 2014-08-04 2016-02-10 中国科学院化学研究所 基于七并稠环单元的a-d-a共轭分子及其制备方法和应用
KR20160041391A (ko) * 2014-10-07 2016-04-18 덕산네오룩스 주식회사 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
CN106366095A (zh) * 2016-08-30 2017-02-01 苏州大学 一种基于多稠环类的场效应晶体管材料及其制备方法和应用
CN107298758A (zh) * 2017-07-03 2017-10-27 中国科学院化学研究所 一种窄带隙n‑型聚合物受体及其制备方法与应用
CN109134513A (zh) * 2018-09-10 2019-01-04 中南大学 一种稠环苯并噻二唑基非富勒烯受体材料及其制备方法和应用
JP2019019083A (ja) * 2017-07-18 2019-02-07 株式会社日本触媒 縮合多環式化合物
WO2019206926A1 (en) * 2018-04-27 2019-10-31 Merck Patent Gmbh Organic semiconducting polymers

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104169347A (zh) * 2012-03-16 2014-11-26 默克专利股份有限公司 共轭聚合物
CN103848967A (zh) * 2012-11-28 2014-06-11 海洋王照明科技股份有限公司 一种含噻吩并噻吩、苯并噻二唑和环戊并二噻吩聚合物及其制备与应用
CN104211912A (zh) * 2013-05-29 2014-12-17 海洋王照明科技股份有限公司 共轭聚合物及其制备方法与应用
CN104557968A (zh) * 2013-10-29 2015-04-29 中国科学院化学研究所 基于二噻吩并引达省的a-d-a共轭分子及其制备方法和应用
CN105315298A (zh) * 2014-08-04 2016-02-10 中国科学院化学研究所 基于七并稠环单元的a-d-a共轭分子及其制备方法和应用
KR20160041391A (ko) * 2014-10-07 2016-04-18 덕산네오룩스 주식회사 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
CN106366095A (zh) * 2016-08-30 2017-02-01 苏州大学 一种基于多稠环类的场效应晶体管材料及其制备方法和应用
CN107298758A (zh) * 2017-07-03 2017-10-27 中国科学院化学研究所 一种窄带隙n‑型聚合物受体及其制备方法与应用
JP2019019083A (ja) * 2017-07-18 2019-02-07 株式会社日本触媒 縮合多環式化合物
WO2019206926A1 (en) * 2018-04-27 2019-10-31 Merck Patent Gmbh Organic semiconducting polymers
CN109134513A (zh) * 2018-09-10 2019-01-04 中南大学 一种稠环苯并噻二唑基非富勒烯受体材料及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JUN YUAN ET AL.: "Fused Benzothiadiazole: A Building Block for n‐Type Organic Acceptor to Achieve High‐Performance Organic Solar Cells", 《ADVANCED MATERIALS》 *
LING HONG: "Eco‐Compatible Solvent‐Processed Organic Photovoltaic Cells with Over 16% Efficiency", 《ADVANCED MATERIALS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112552489A (zh) * 2020-11-09 2021-03-26 山东师范大学 一种非对称非富勒烯化合物及其制备方法与应用
CN115386069A (zh) * 2022-09-29 2022-11-25 位速科技股份有限公司 共聚物、有源层及有机光伏元件
CN115386069B (zh) * 2022-09-29 2024-03-12 位速科技股份有限公司 共聚物、有源层及有机光伏元件

Also Published As

Publication number Publication date
CN110862518B (zh) 2021-05-14

Similar Documents

Publication Publication Date Title
CN110734539B (zh) 基于五元或七元芳香稠环的聚合物及其在有机光电器件中的应用
EP2530084B1 (en) Copolymer containing fluorenylporphyrin-anthracene, preparation method and use thereof
WO2017107573A1 (zh) 基于七并稠环单元的共轭大分子及其制备方法和在太阳能电池中的应用
CN104140521A (zh) 宽吸收谱的三元共轭聚合物给体材料及其制备方法和用途
Fan et al. Improved photovoltaic performance of a 2D-conjugated benzodithiophene-based polymer by the side chain engineering of quinoxaline
CN110862518B (zh) 基于多元稠环结构的多元共聚物及其在有机光电器件中的应用
Gu et al. Design, synthesis and photovoltaic properties of two π-bridged cyclopentadithiophene-based polymers
CN111138640B (zh) 受体聚合物、光活性层、能量器件及制备方法与应用
CN109134525A (zh) 一种a-d-a型光伏小分子及其制备方法与应用
CN111234183B (zh) 一种含苝二酰亚胺单元的单组分活性层光伏材料
CN112661940B (zh) 基于噻吩并噻二唑的n型水/醇溶共轭聚电解质及其制备与应用
CN112646129B (zh) 含苯并双噻二唑的n型水/醇溶共轭聚电解质及其制备与应用
CN109749061B (zh) 联受体型聚合物光伏材料及其制备和应用
CN109776769B (zh) 一种基于噻吩、苝二酰亚胺和异靛蓝单元的三元共聚物及其制备方法
KR20180009547A (ko) 유기 태양전지용 공액 고분자 및 이의 제조방법
CN110982047B (zh) 一类引达省并二呋喃基有机太阳能电池给体材料、其制备方法及应用
JP5701453B2 (ja) ジフルオロベンゾトリアゾリル太陽電池材料、調合法、およびその使用方法
KR101400077B1 (ko) 신규한 중합체, 이의 제조방법 및 이를 함유하는 유기 광전자 소자
CN112646130A (zh) 基于双自由基苯并双噻二唑的n型水/醇溶共轭聚电解质及其制备与应用
Chau et al. Complementary absorbing ternary blend containing structural isomeric donor polymers for improving the performance of PC61BM-based indoor photovoltaics
JP2015510948A (ja) チオフェン−ベンゼン−チオフェン単位を含有するポリマー、その製造方法、および太陽電池デバイス
KR101821971B1 (ko) 랜덤 삼원 공중합체 형태의 전자 수용체 고분자, 그의 제조방법 및 이를 포함하는 반전형 고분자 태양전지
KR101744523B1 (ko) 싸이에노피롤 유도체를 포함하는 공중합체 및 그를 포함하는 유기전자소자
CN115353611B (zh) 一种含抗氧化剂侧链的共轭聚合物和制备方法及其应用
CN108929430A (zh) 基于苝二酰亚胺与苯炔共聚的n型共轭聚合物及其在有机光电器件中的应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant