CN108059714A - 一种含不对称萘二杂环共轭聚合物及其在有机光电器件中的应用 - Google Patents

一种含不对称萘二杂环共轭聚合物及其在有机光电器件中的应用 Download PDF

Info

Publication number
CN108059714A
CN108059714A CN201810038792.XA CN201810038792A CN108059714A CN 108059714 A CN108059714 A CN 108059714A CN 201810038792 A CN201810038792 A CN 201810038792A CN 108059714 A CN108059714 A CN 108059714A
Authority
CN
China
Prior art keywords
naphthalene
conjugated polymer
asymmetric
heterocyclic conjugated
optic device
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.)
Pending
Application number
CN201810038792.XA
Other languages
English (en)
Inventor
黄飞
胡志诚
应磊
曹镛
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 Institute of Collaborative Innovation
Original Assignee
South China Institute of Collaborative Innovation
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 Institute of Collaborative Innovation filed Critical South China Institute of Collaborative Innovation
Priority to CN201810038792.XA priority Critical patent/CN108059714A/zh
Publication of CN108059714A publication Critical patent/CN108059714A/zh
Pending legal-status Critical Current

Links

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
    • C08G61/125—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 oxygen 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
    • 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
    • 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
    • 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
    • C08G2261/124—Copolymers alternating
    • 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
    • C08G2261/18—Definition of the polymer structure conjugated
    • 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
    • C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
    • 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
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
    • 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
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • 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
    • C08G2261/95—Use in organic luminescent diodes
    • 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)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

本发明属于高分子光电材料技术领域，公开了一种含不对称萘二杂环共轭聚合物及其在有机光电器件中的应用。本发明的含不对称萘二杂环共轭聚合物结构如下：其中，聚合度n为小于100万的正整数；A1、A2为不同的五元杂环；R1、R2、R3、R4相同或不同的分别为烷基链；D为给电子共轭单元。本发明还提供上述含不对称萘二杂环共轭聚合物在有机光电器件中的应用。本发明的共轭聚合物主链为不对称萘二杂环和给电子共轭单元。不对称萘二杂环具有刚性的平面结构，利于更好的π‑π堆积效应、更好的平面性和缺电子性，有利于电荷的传输，可以应用于高迁移率电子器件，得到更好的性能。

Description

一种含不对称萘二杂环共轭聚合物及其在有机光电器件中的 应用
技术领域
本发明属于高分子光电材料技术领域，特别涉及一种含不对称萘二杂环共轭聚合物及其在有机光电器件中的应用。
背景技术
随着全球对于能源需求的逐年增加，石油、煤炭等传统能源的日益枯竭，以及对保护地球生态环境的需要，全世界越来越多的科学家将研究集中在氢气、太阳能等取之不尽用之不竭的可再生清洁能源。
已经成熟的无机硅、砷化镓、磷化铟等基于无机材料的光伏器件已经在市场上占有主导地位，然而由于其对材料纯度的要求高，加工过程中会产生高能耗及污染等问题，且其价格非常昂贵，因此在追求低成本和绿色环保的今天，其大规模应用受到了限制。
有机光电器件作为一种新型薄膜光伏电池技术，具有全固态、光伏材料性质可调范围宽、可实现半透明、柔性电池、具有大面积低成本制备潜力等突出优点。有机材料的光伏性能可调范围宽，可利用化学手段对材料的能级、载流子迁移率以及吸收等性能进行有效的调控。有机/聚合物光伏器件可采用打印、印刷等方法进行加工，可借鉴传统塑料的加工工艺，通过卷对卷滚动加工流程制造大面积、柔性的薄膜光伏器件，该生产工艺能够有效降低光伏电池的制造成本。有机光电器件几乎不受环境和场地限制，在许多场合可将光能转换为电能，同时与无机半导体光伏器件有非常强的互补性，无疑具有巨大的商业开发价值和市场竞争力。因此有机光电器件的研究引起了广泛关注，以有机光电器件为核心的科学研究已经成为一个世界范围内竞争激烈的材料科学前沿研究领域。
在众多光电材料中，含苯并杂环基团的光电材料在有机电致发光、有机太阳电池、化学和生物传感器以及有机场效应晶体管等材料中已经得到了广泛的应用。与苯并杂环相比，萘二杂环具有两个苯并杂环相连的结构，因此它具有苯并杂环基本优点的同时，还具有更大的刚性平面、更强的缺电子性。此外，不对称的萘二杂环结构还具有一些特殊性能。本发明设计合成了一系列含不对称萘二杂环有机半导体材料，并将其用于有机光电器件中，展现出了良好的载流子迁移率与器件效率。
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含不对称萘二杂环共轭聚合物。
本发明另一目的在于提供上述含不对称萘二杂环共轭聚合物在有机光电器件中的应用。
本发明的目的通过下述方案实现：
一种含不对称萘二杂环共轭聚合物，结构如下：
其中，聚合度n为小于100万的正整数；A1、A2为不同的五元杂环；R1、R2、R3、R4相同或不同的分别为烷基链；D为给电子共轭单元。
所述的D具有如下结构的一种或一种以上：
进一步地，所述的R1、R2、R3、R4相同或不同的分别为C1～40的直链、支链或者环状烷基链；所述C1～40的直链、支链或者环状烷基链中的一个或一个以上碳原子可被氧原子、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；所述C1～40的直链、支链或者环状烷基链中的一个或一个以上氢原子可被氟原子、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。
进一步地，所述的A1、A2不同的分别具有如下结构的一种或一种以上：
本发明的含不对称萘二杂环共轭聚合物可通过Stille聚合反应得到。
本发明还提供上述含不对称萘二杂环共轭聚合物在有机光电器件中的应用。所述有机光电器件的结构如图1所示，由衬底、阳极、阳极界面层、光吸收层、阴极界面层、阴极依次层叠构成。具体为所述有机光电器件中的光吸收层含有本发明所述的含不对称萘二杂环共轭聚合物。
所述有机光电器件中，阳极材料优选为铝、银、金、钙/铝合金或钙/银合金、氧化锡铟(ITO)。
所述有机光电器件中，阳极界面层优选为有机共轭聚合物(如聚3,4-乙撑二氧噻吩/聚苯乙烯磺酸盐)或无机半导体。
所述有机光电器件中，阴极优选为金属、金属氧化物(如氧化铟锡导电膜(ITO)、掺杂二氧化锡(FTO)、氧化锌(ZnO)、铟镓锌氧化物(IGZO))和石墨烯及其衍生物中的至少一种。
所述有机光电器件中，衬底优选为玻璃、柔性材料(如聚酰亚胺、聚对苯二甲酸乙二醇酯、乙烯对苯二甲酸酯、聚萘二甲酸乙二醇酯或其他聚酯材料)、金属、合金和不锈钢薄膜中的至少一种。
本发明的共轭聚合物主链为不对称萘二杂环和给电子共轭单元。不对称萘二杂环具有刚性的平面结构，利于更好的π-π堆积效应、更好的平面性和缺电子性，有利于电荷的传输，可以应用于高迁移率电子器件，得到更好的性能。
本发明相对于现有技术，具有如下的优点及有益效果：
(1)本发明设计合成了一系列新型不对称萘二杂环有机半导体材料，这类有机半导体可以很好的调节光电性质，具有良好的光电性能。
(2)所述的新型不对称萘二杂环共轭聚合物具有良好的热稳定性。
(3)不对称萘二杂环具有刚性的平面结构，利于更好的π-π堆积效应、更好的平面性和缺电子性，有利于电荷的传输，可以应用于高迁移率电子器件，得到更好的性能。
附图说明
图1为有机光电器件结构示意图。
图2为本发明新型不对称萘二杂环共轭聚合物(P1、P2、P3)的紫外-可见光-近红外吸收谱图。
图3为电池结构为ITO阴极/阳极界面层/活性层/阴机界面层/阳极(正装结构)时，活性层含本发明共轭聚合物(P1、P2、P3)时电池器件的电流-电压曲线图。
图4为本发明的共轭聚合物的热失重曲线。
具体实施方式
下面结合实施例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。
下列实施例中涉及的物料均可从商业渠道获得。
实施例1
(1)单体M1按照文献[Polymer,2015,67:40-46.]公开的方法合成。
(2)单体M2，M3，M4按照文献[Chemistry of Materials,2015,27(15):5230-5237.]公开的方法合成。
(3)聚合物P1、P2、P3的合成：
将单体M1(0.5mmol)和单体M2(0.5mmol)加入到25mL两口烧瓶中，通入氮气保护，加入8mL甲苯。抽换气两次后加入5mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P1，产率74.5％。1H NMR(CDCl3 500MHz):δ:7.20-6.90(m,6H),4.13-3.50(m,6H),2.00-1.85(m,4H),1.05-1.30(br,26H),0.87(t,15H).GPC:Mn＝45.8KDa,Mw＝96.2KDa,PDI＝2.1.Elem.Anal.:C,67.86；H,7.12；N,7.61；S,17.42.
将单体M1(0.5mmol)和单体M3(0.5mmol)加入到25mL两口烧瓶中，通入氮气保护，加入10mL甲苯。抽换气两次后加入7mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P2，产率72.9％。1H NMR(CDCl3 500MHz):δ:7.18-6.85(m,6H),4.12-3.60(m,6H),2.05-1.85(m,4H),1.05-1.30(br,26H),0.87(t,15H).GPC:Mn＝47.5KDa,Mw＝118.7KDa,PDI＝2.5.Elem.Anal.:C,70.31；H,7.38；N,7.88；O,3.60；S,10.83.
将单体M1(0.5mmol)和单体M4(0.5mmol)加入到25mL两口烧瓶中，通入氮气保护，加入10mL甲苯。抽换气两次后加入5mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P3，产率71.2％。1H NMR(CDCl3 500MHz):δ:7.21-6.92(m,6H),4.12-3.51(m,6H),2.02-1.81(m,4H),1.05-1.30(br,26H),0.87(t,15H).GPC:Mn＝48.7KDa,Mw＝136.4KDa,PDI＝2.8.Elem.Anal.:C,69.06；H,7.24；N,7.74；O,1.77；S,14.18.
将所得的聚合物进行溶液的吸收光谱的测定，如图2所示。从溶液的浓度(0.02mg/ml)和所测得的吸收值可以计算出聚合物P1、P2、P3的吸收系数。P1、P2、P3在最高峰的吸收系数分别为1.37×105cm-1，1.21×105cm-1，1.23×105cm-1。
合成路线如下：
实施例2
以实施例1所合成的共轭聚合物P1、P2、P3作为电子给体在有机光电器件(ITO阳极/阳极界面层/活性层/阴机界面层/阴极)中应用
将ITO导电玻璃，方块电阻～20欧/平方厘米，预切成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，氮气吹哨后置于恒温烘箱备用。在ITO上旋凃一层20nm厚的PEDOT:PSS，然后旋涂活性层材料P1/PC71BM，P2/PC71BM，P3/PC71BM，厚度均为100nm。然后旋涂一层5nm厚的PFN-Br，最后蒸镀Al电极。所有制备过程均在提供氮气氛围的手套箱内进行。所制备的正装电池器件的电流-电压曲线如图3所示，相关的数据在表1中列出。图4为本发明的共轭聚合物的热失重曲线。
表1本发明共轭聚合物作为电子给体材料时，有机光电器件的性能参数
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 (10)

1.一种含不对称萘二杂环共轭聚合物，其特征在于结构如下：
其中，聚合度n为小于100万的正整数；A1、A2为不同的五元杂环；R1、R2、R3、R4相同或不同的分别为烷基链；D为给电子共轭单元。
2.根据权利要求1所述的含不对称萘二杂环共轭聚合物，其特征在于所述的D具有如下结构的一种或一种以上：
3.根据权利要求1所述的含不对称萘二杂环共轭聚合物，其特征在于：所述的R1、R2、R3、R4相同或不同的分别为C1～40的直链、支链或者环状烷基链。
4.根据权利要求3所述的含不对称萘二杂环共轭聚合物，其特征在于：所述C1～40的直链、支链或者环状烷基链中的一个或一个以上碳原子被氧原子、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。
5.根据权利要求3所述的含不对称萘二杂环共轭聚合物，其特征在于：所述C1～40的直链、支链或者环状烷基链中的一个或一个以上氢原子被氟原子、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。
6.根据权利要求1所述的含不对称萘二杂环共轭聚合物，其特征在于：所述的A1、A2不同的分别具有如下结构的一种或一种以上：
7.根据权利要求1所述的含不对称萘二杂环共轭聚合物，其特征在于通过Stille聚合反应得到。
8.权利要求1～7任一项所述的含不对称萘二杂环共轭聚合物在有机光电器件中的应用。
9.根据权利要求8所述的含不对称萘二杂环共轭聚合物在有机光电器件中的应用，其特征在于：所述有机光电器件由衬底、阳极、阳极界面层、光吸收层、阴极界面层、阴极依次层叠构成。
10.根据权利要求9所述的含不对称萘二杂环共轭聚合物在有机光电器件中的应用，其特征在于：所述的光吸收层含有权利要求1～7任一项所述的含不对称萘二杂环共轭聚合物。
CN201810038792.XA 2018-01-16 2018-01-16 一种含不对称萘二杂环共轭聚合物及其在有机光电器件中的应用 Pending CN108059714A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810038792.XA CN108059714A (zh) 2018-01-16 2018-01-16 一种含不对称萘二杂环共轭聚合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
CN201810038792.XA CN108059714A (zh) 2018-01-16 2018-01-16 一种含不对称萘二杂环共轭聚合物及其在有机光电器件中的应用

Publications (1)

Publication Number Publication Date
CN108059714A true CN108059714A (zh) 2018-05-22

Family

ID=62141688

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810038792.XA Pending CN108059714A (zh) 2018-01-16 2018-01-16 一种含不对称萘二杂环共轭聚合物及其在有机光电器件中的应用

Country Status (1)

Country Link
CN (1) CN108059714A (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012111811A1 (ja) * 2011-02-18 2012-08-23 コニカミノルタホールディングス株式会社 有機光電変換素子および太陽電池
US20140319509A1 (en) * 2011-11-15 2014-10-30 Konica Minolta, Inc. Organic photoelectric conversion element, and solar cell and optical sensor array each using same
JP2016017117A (ja) * 2014-07-07 2016-02-01 国立研究開発法人理化学研究所 高分子化合物、有機半導体材料、光電変換素子及びトランジスタ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012111811A1 (ja) * 2011-02-18 2012-08-23 コニカミノルタホールディングス株式会社 有機光電変換素子および太陽電池
US20140319509A1 (en) * 2011-11-15 2014-10-30 Konica Minolta, Inc. Organic photoelectric conversion element, and solar cell and optical sensor array each using same
JP2016017117A (ja) * 2014-07-07 2016-02-01 国立研究開発法人理化学研究所 高分子化合物、有機半導体材料、光電変換素子及びトランジスタ

Similar Documents

Publication Publication Date Title
CN103956431B (zh) 一种溶液加工的有机‑无机平面异质结太阳电池及其制备
CN109749059A (zh) 一种主链含氰基茚酮的稠环n型聚合物及其应用
CN108276560B (zh) 基于主链含苯并三唑酰亚胺和引达省氰基茚酮的嵌段共聚物及在单组分有机太阳电池的应用
CN106986982A (zh) 三键连接的水醇溶共轭聚合物及其在有机光电器件中的应用
CN109449299B (zh) 光电活性层以及在柔性光电-压电混合能源电池中的应用
CN109021214A (zh) 含寡聚乙二醇基侧链修饰萘二酰亚胺单元的n-型共轭聚合物及其在有机光电器件中的应用
CN105237745A (zh) 含季膦盐基团共轭聚电解质及其在有机光电器件中的应用
CN107325266A (zh) 含醌式结构的n型共轭聚合物及其在有机光电器件中的应用
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
CN108034042B (zh) 一种主链给体-侧链受体型共轭聚合物及其制备和应用
Qiu et al. An asymmetric small molecule based on thieno [2, 3-f] benzofuran for efficient organic solar cells
CN108084405A (zh) 基于主链结构为萘二酰亚胺和引达省氰基茚酮的嵌段共聚物及其在有机光伏器件中的应用
CN107793423B (zh) 新型n型醌式结构小分子及其在有机光电器件中的应用
CN114883500A (zh) 一种非卤素溶剂加工的基于聚噻吩体系的有机太阳电池及其制备方法
CN107674183B (zh) 含萘[1,2-c；5,6-c]二[1,2,5]噻二唑的共轭聚合物及制备方法和应用
CN107674180A (zh) 基于共轭π桥相连呋喃的n型共轭聚合物及其在有机光电器件中的应用
CN112646130B (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
CN109244242A (zh) 一种有机太阳电池及其制备方法
CN105384930B (zh) 共轭-非共轭n型聚电解质及其在有机光电器件中的应用
CN109749060A (zh) 一种侧链支化点可调的萘酰亚胺n型共轭聚合物及其应用
CN107778457A (zh) 基于连呋喃的n型共轭聚合物及其在有机光电器件中的应用
CN109694463B (zh) 含硅氧烷侧链的萘二酰亚胺n型共聚物及其在有机光电器件中的应用
CN108084406B (zh) 基于侧链含吸光型受体的n型共轭聚合物及其制备和应用
CN105720199A (zh) 一种大面积有机薄膜太阳能电池及其制备方法
CN108059714A (zh) 一种含不对称萘二杂环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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20180522