WO2015169083A1 - 含s,s-二氧-二苯并噻吩单元的电子给体聚合物及其应用 - Google Patents

含s,s-二氧-二苯并噻吩单元的电子给体聚合物及其应用 Download PDF

Info

Publication number
WO2015169083A1
WO2015169083A1 PCT/CN2014/092731 CN2014092731W WO2015169083A1 WO 2015169083 A1 WO2015169083 A1 WO 2015169083A1 CN 2014092731 W CN2014092731 W CN 2014092731W WO 2015169083 A1 WO2015169083 A1 WO 2015169083A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
polymer
dibenzothiophene
dioxy
electron donor
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.)
Ceased
Application number
PCT/CN2014/092731
Other languages
English (en)
French (fr)
Inventor
杨伟
何锐锋
徐进
张斌
吴宏滨
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 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
Publication of WO2015169083A1 publication Critical patent/WO2015169083A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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

Definitions

  • the invention relates to an electron donor polymer containing S,S-dioxy-dibenzothiophene unit and application thereof, and belongs to the technical field of photoelectric materials.
  • organic solar cells As a new type of energy device, organic solar cells have received extensive attention due to their simple production process, low manufacturing cost, and easy preparation of large-area flexible batteries. Among them, organic solar cells based on bulk heterojunction structure have become a research hotspot in this field in recent years due to high photoelectric conversion efficiency.
  • the structural feature of the bulk heterojunction organic solar cell is that the active layer of the battery device is prepared by blending the donor and the acceptor material, so that the donor and the acceptor material can easily form a double-connected channel, increasing the donor and the acceptor.
  • the contact area and the degree of phase separation increase the photoelectric conversion efficiency of the device.
  • S,S-dioxy-dibenzothiophene units are a kind of conjugated groups with rigid planar structure, wide band gap and strong electronegativity. Because of their good fluorescence, they have been widely used in the field of luminescent materials.
  • the copolymerization of S,S-dioxy-dibenzothiophene unit with a strong electron donating group can effectively reduce the intramolecular energy transfer between the electron donating unit and the S,S-dioxy-dibenzothiophene unit.
  • the polymer has a band gap to give a medium band gap polymer donor material.
  • the photoelectric properties of the synthesized medium (narrow) band gap polymer solar cell donor materials are effectively adjusted.
  • Solar cell devices show superior performance and broad application prospects.
  • containing S, S-diox The electron donor polymer of the dibenzothiophene unit has a high hole mobility and has certain application potential in the field of the effect tube device.
  • the object of the present invention is to provide a method for preparing a novel electron donor polymer containing S,S-dioxy-dibenzothiophene unit and an effective adjustment of electron donor polymerization for the defects of current electron donor polymer materials.
  • Embodiments of the energy band gap and photoelectron properties of the object are to provide a method for preparing a novel electron donor polymer containing S,S-dioxy-dibenzothiophene unit and an effective adjustment of electron donor polymerization for the defects of current electron donor polymer materials.
  • the electron donor polymer containing the S,S-dioxy-dibenzothiophene unit of the present invention has the following chemical formula:
  • R 1 and R 2 are hydrogen, an alkyl group having 1 to 30 carbon atoms, or one or more carbon atoms thereof are bonded to an oxygen atom, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an amino group, a carbonyl group or a carboxyl group. a nitro group, a phenyl group, a thienyl group, or a hydrogen atom is substituted by a halogen atom; the A unit has one or more of the following chemical structures:
  • X 1 and X 2 are N, O, S or Se
  • X 3 is H or F
  • R 3 and R 4 are hydrogen, fluorine or an alkoxy chain of 1 to 30 carbon atoms
  • R 5 is 1 An alkyl chain or an alkylphenyl chain of up to 30 carbon atoms.
  • Electron donor polymers containing S,S-dioxy-dibenzothiophene units are used in organic solar cells or in organic field effect transistor devices.
  • the present invention has the following advantages:
  • S, S-dioxy-dibenzothiophene monomer is easy to synthesize and purify, and the raw material price is low, which is favorable for scale production and production;
  • Electron donor polymers containing S,S-dioxy-dibenzothiophene units have good solubility and thermal stability in common organic solvents such as chloroform, chlorobenzene and o-dichlorobenzene.
  • Deep HOMO energy level and high hole mobility, high light absorption coefficient and high photoelectric response, etc. have high photoelectric conversion efficiency in organic solar cell devices, and have good application in organic field effect transistor. Electric field response performance.
  • Figure 1 is a graph of thermogravimetric analysis of a polymer
  • Figure 2 is an absorption spectrum diagram of a unit thickness of a polymer film
  • Figure 3 is a diagram showing the oxidation process of the electrochemical curve of the polymer
  • Figure 4 is a current-voltage curve of a polymer solar cell
  • Figure 5 is an AFM diagram of PBDT-DTOBT: PC 71 BM (a, b) and PBDT-SO-DTOBT: PC 71 BM (c, d) film;
  • Figure 6 is a plot of the output (a, c) and transfer (b, d) characteristics of an organic field effect transistor based on polymers PIDT-FSO and PIDT-DHTSO.
  • 1,2-b:5,6-b']-dithiophene (0.616 g, 0.5 mmol), 3,7-dibromo-2,8-difluoro-S,S-dioxy-dibenzothiophene ( 0.174 g, 0.5 mmol), tris(dibenzylideneacetone)dipalladium (0.006 g), tris(2-tolyl)phosphine (0.012 g and toluene (4 mL), microwave reaction at 180 ° C for 45 minutes, the reaction was terminated.
  • 1,2-b:5,6-b']-dithiophene (0.616 g, 0.5 mmol), 3,7-bis(4-hexylthiophene-2-bromo)-S,S-dioxy-dibenzo Thiophene (0.353 g, 0.5 mmol), tris(dibenzylideneacetone)dipalladium (0.006 g), tris(2-tolyl)phosphine (0.012 g) and toluene (4 mL), microwave reaction at 180 ° C for 45 minutes, ending After the reaction is cooled to room temperature, the reaction solution is precipitated in methanol, subjected to Soxhlet extraction with methanol and acetone, and subjected to column chromatography with chloroform as an eluent, and dried to obtain an orange-red solid.
  • the first time was capped, 2-tributyltinthiophene (0.1g) was added, after 12 hours of reaction, the second time was blocked, 2-bromothiophene (0.2g) was added, and the reaction was further carried out for 12 hours to terminate the reaction.
  • the reaction solution was precipitated into methanol, then subjected to Soxhlet extraction with methanol and acetone, and subjected to column chromatography with chlorobenzene as an eluent, and dried to give a brown solid. Yield: 60%.
  • PBDT-DTOBT and PICz-DTOBT respectively represent S, S-II corresponding to PBDT-SO-DTOBT and PICz-SON-DTOBT.
  • SO oxy-dibenzothiophene
  • the absorption spectrum of the polymer film obtained by the above preparation is shown in Fig. 2. It can be seen from the figure that the polymer containing the SO unit has a higher light absorptivity than the polymer containing no SO unit, including 2, 8
  • the polymer of the difluoro-substituted SO unit has a higher light absorption than the polymer of the same type, which is advantageous for the improvement of the short-circuit current of the related polymer solar cell device.
  • the oxidation process of the electrochemical curve of the above prepared polymer is shown in Figure 3, wherein the polymer containing the SO unit has a deeper HOMO level than the polymer containing no SO unit, and contains 2,8-difluoro-substituted
  • the polymer of the SO unit has a deeper HOMO level than the same type of polymer, which is beneficial to the increase in the open circuit voltage of the associated polymer solar cell device.
  • Table 1 shows the physical properties of the relevant polymers. As can be seen from Table 1, the polymers all have a higher number average molecular weight and a smaller molecular weight dispersion coefficient.
  • the SO unit-containing polymer has a relatively lower HOMO level, higher absorbance, and hole mobility than the polymer without the SO unit.
  • As an electron donor material it is beneficial to increase the open circuit voltage and short circuit current of the solar cell device; as an active layer, it is beneficial to improve the hole mobility of the organic field effect transistor.
  • the ITO glass was ultrasonically cleaned and treated with oxygen plasma.
  • the sheet resistance of the ITO glass was 10 ⁇ / ⁇ , and an interface layer PFN was spin-coated on the ITO to polymerize the above polymer with PC 61 BM (or PC 71 BM).
  • the solution is separately prepared into a solution, mixed, spin-coated on the PFN layer to form an active layer, a layer of MoO 3 is deposited on the active layer, and finally an Al metal electrode is vapor-deposited.
  • the battery characteristics were measured under irradiation of AM 1.5 simulated sunlight.
  • ITO indium tin oxide conductive glass
  • PC 61 BM is the abbreviation of "methanofullerene [6,6]-phenyl C61-butyric acid methyl ester” in English
  • PFN is poly[9,9-dioctylfluorene-9 , 9-bis(N,N-dimethylaminopropyl) hydrazine].
  • the current-voltage curve of the polymer solar cell prepared above is shown in Fig. 4. It can be seen that the polymer containing the SO unit generally has a high open circuit voltage, and the former is relative to the polymer containing no SO unit. Has better photoelectric response characteristics.
  • a polymer containing a 2,8-difluoro-substituted SO unit has a higher open circuit voltage than a polymer of the same type, and a polymer having a side chain polar group in place of the SO unit is more than a polymer of the same type without the unit.
  • the material has a high short-circuit current and an open circuit voltage at the same time, and has certain interface modification characteristics.
  • the AFM height and phase diagrams for the polymer PBDT-DTOBT:PC 71 BM and PBDT-SO-DTOBT:PC 71 BM films are shown in Figures 5(a,b) and (c,d), respectively.
  • the mixed film has a more uniform phase separation, which is beneficial to increase the effective area of the bulk heterojunction, thereby improving the photoelectric performance of the related device.
  • Table 2 shows the photovoltaic characteristics of polymer solar cells, in which the polymer containing SO unit exhibits relatively high open circuit voltage, short circuit current, fill factor and photoelectric conversion in the same type of device than the same type of polymer without SO unit. effectiveness.
  • the photoelectric conversion efficiency of the polymer PIDT-DHTSO is currently the highest reported band gap exceeding 2.2 eV.
  • ITO / PFN / polymer PC 61 BM (1: 3, w / w) / MoO 3 / Al;
  • ITO / PFN / polymer PC 71 BM (1: 3, w / w) / MoO 3 / Al;
  • ITO / ZnO / PFN / polymer PC 71 BM (1: 2, w / w) / MoO 3 / Al;
  • ITO/PEDOT/polymer PC 71 BM (1:3, w/w)/Al.
  • An organic field effect diode uses a top contact structure with silver as the primary and drain electrodes.
  • High n-type doped silicon and thermally grown silicon oxide 300 nm were used as the bottom gate and gate dielectric layers, respectively.
  • Octyltrichlorosilane (OTS) serves as the interface material for the gate dielectric layer.
  • a polymer film 80 nm was spin-coated on the OTS layer and then annealed at 120 ° C for 10 min.
  • a silver electrode layer 60 nm was plated on the polymer thin by vacuum evaporation.
  • the OFET device structure is: Si/SiO 2 /OTS/polymer/Ag, and the device aspect ratio is 60:1.
  • the OFET device performance test was performed on the Aglient 4155C platform in an atmospheric environment.
  • the output (a, c) and transfer (b, d) characteristic curves of the organic field effect transistor of the polymer PIDT-FSO and PIDT-DHTSO are shown in Fig. 6. From the characteristic curve, it is found that the SO-containing polymer exhibits good electric field response characteristics in the organic field effect transistor, and the calculated hole mobility is above 1 ⁇ 10 -4 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Photovoltaic Devices (AREA)

Abstract

本发明公开含S,S-二氧-二苯并噻吩单元的电子给体聚合物及其应用。所述电子给体聚合物主链中含有S,S-二氧-二苯并噻吩单元。通过Stille、Suzuki等聚合方法，构造出新型的D-A结构共轭聚合物。S,S-二氧-二苯并噻吩单元平面性好和电负性高等特性，赋予聚合物具备较深的HOMO能级、强的分子间相互作用、高吸光系数、高迁移率以及较高的光电响应等性能，使相关聚合物材料在有机太阳电池或有机场效应晶体管器件中具有广泛的应用前景。

Description

含S,S-二氧-二苯并噻吩单元的电子给体聚合物及其应用 技术领域
本发明涉及含S,S-二氧-二苯并噻吩单元的电子给体聚合物及其应用，属于光电材料技术领域。
背景技术
有机太阳电池作为一类新型的能源器件，由于生产工艺简单，制造成本低，易制备大面积柔性电池而得到了广泛关注。其中，基于本体异质结结构的有机太阳电池由于光电转换效率高而成为近年来该领域的研究热点。本体异质结有机太阳电池的结构特点在于电池器件的活性层制备是通过给体与受体材料进行共混，使给体与受体材料容易形成双联通沟道，增加给体和受体的接触面积以及相分离的程度，从而提高器件的光电转换效率。
目前，有机太阳电池单活性层器件的效率已经接近10％，但由于单活性层器件的短路电流和开路电压存在着一定的局限性，通过单活性层器件进一步提高效率，有一定的困难。Yang等[Nat.Commun.2013,4,doi:10.1038/ncomms2411]通过两个或多个活性层进行串联的方法，制备叠层器件，能大大提高器件效率。从活性层材料的角度上考虑，需要每个活性层材料能够实现吸收光谱的互补，从而使整个器件的光吸收尽量覆盖太阳光发射范围，降低光子能量损失，同时提高器件的开路电压，实现光电转换效率的提高。因此，高效的中等带隙和窄带隙聚合物太阳电池给体材料的开发显得尤为重要。
S,S-二氧-二苯并噻吩单元是一类具有刚性平面结构、宽带隙和强电负性的共轭基团，由于其荧光性好，已被广泛应用到有发光材料领域中。S,S-二氧-二苯并噻吩单元与强供电子基团进行共聚，由于供电子单元与S,S-二氧-二苯并噻吩单元间形成分子内能量转移作用，能有效地降低聚合物能带隙，得到中等带隙的聚合物给体材料。基于S,S-二氧-二苯并噻吩单元的平面性好和电负性高等特点，使合成的中等(窄)带隙聚合物太阳电池给体材料的光电性能得到有效的调节，在有机太阳电池器件中显示出优越的性能和广阔的应用前景。同时，含S,S-二氧 -二苯并噻吩单元的电子给体聚合物具有较高的空穴迁移率，在有机场效应管器件具有一定的应用潜力。
发明内容
本发明的目的在于针对目前电子给体聚合物材料开发的不足，提供含S,S-二氧-二苯并噻吩单元的新型电子给体聚合物的制备方法和一种有效调节电子给体聚合物的能带隙和光电子性能的实施方案。
本发明的目的还在于提供所述的含S,S-二氧-二苯并噻吩单元的电子给体聚合物在制备有机太阳电池或有机场效应晶体管中的应用。
本发明所述的含S,S-二氧-二苯并噻吩单元的电子给体聚合物，具有如下化学结式：
Figure PCTCN2014092731-appb-000001
其中：x、y为摩尔分数，0<x≤1，0≤y<1，x+y＝1；聚合度n：1～300；R为H、F、烷氧基或末端含极性基团(包括胺基、磷酸酯基或氰基)的烷氧基链；D单元具有如下化学结构中的一种以上：
Figure PCTCN2014092731-appb-000002
其中，R1、R2为氢、1～30个碳原子数的烷基、或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、硝基、苯基、噻吩基取代，或氢原子被卤素原子取代；A单元具有如下化学结构中的一种以上：
Figure PCTCN2014092731-appb-000003
Figure PCTCN2014092731-appb-000004
其中，X1、X2为N、O、S或Se，X3为H或F，R3、R4为氢、氟或1～30个碳原子数的烷氧基链，R5为1～30个碳原子数的烷基链或烷苯基链。
含S,S-二氧-二苯并噻吩单元的电子给体聚合物应用于有机太阳电池或有机场效应管器件中。
与已有技术相比，本发明具有以下优点：
1)S,S-二氧-二苯并噻吩单体的合成、纯化容易，原料价格低廉，有利于规模制备生产；
2)含S,S-二氧-二苯并噻吩单元的电子给体聚合物在常用有机溶剂(如氯仿、氯苯和邻二氯苯等)中有较好的溶解性、热稳定性、较深的HOMO能级及较高的空穴迁移率，高吸光系数及较高的光电响应等，应用在有机太阳电池器件具有较高的光电转换效率，应用在有机场效应管晶体管中具有良好的电场响应性能。
附图说明
图1为聚合物的热失重分析曲线图；
图2为聚合物薄膜单位厚度的吸收光谱图；
图3为聚合物电化学曲线的氧化过程图；
图4为聚合物太阳电池的电流-电压曲线；
图5为PBDT-DTOBT:PC71BM(a,b)和PBDT-SO-DTOBT:PC71BM(c,d)薄膜的AFM图；
图6为基于聚合物PIDT-FSO和PIDT-DHTSO的有机场效应晶体管的输出(a,c)和转移(b,d)特征曲线。
具体实施方式
以下通过实施例对S,S-二氧-二苯并噻吩衍生物单体的合成作进一步的说明，但本发明将不限于所列之例。
实施例1：
3,7-二溴-S,S-二氧-二苯并噻吩的制备路线
(1)S,S-二氧-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000005
在500ml的三口圆底烧瓶，加入二苯并噻吩(18.4g，100mmol)、乙酸(200ml)和双氧水(50mL)，加热回流反应过夜，反应结束后待反应温度降到室温，反应液析出大量晶体，抽滤，依次用乙酸和乙醇洗涤滤渣数次。烘干，得到无色针状晶体17.3g,产率：80％。
(2)3,7-二溴-S,S-二氧-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000006
在500ml的单口烧瓶，加入S,S-二氧-二苯并噻吩(10.8g，50mmol)、浓硫酸(150ml)，搅拌溶解后，避光下缓慢加入N-溴代丁二酰亚胺(NBS，22.3g，125mmol)。强力搅拌反应24小时，停止反应，将反应物缓慢倒入冰水中，有大量固体析出，抽滤，依次用碳酸氢钠水溶液、水和乙醇洗涤滤渣，干燥后，滤渣用氯苯重结晶，得到无色晶体9.4g，产率：50％。
实施例2：
2,8-二氟-3,7-二溴-S,S-二氧-二苯并噻吩的制备路线
(1)2,8-二氟-S,S-二氧-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000007
在500ml的三口圆底烧瓶，加入4,4’-二氟二苯砜(15.2g，60mmol)、氯化亚酮(20.2g,150mmol)和无水四氢呋喃(THF)(300ml)，搅拌降温到-78℃后，滴加入正丁基锂溶液(2.5M in THF,53mL,132mmol)，滴加完毕后，让反应缓慢升温到20℃，再反应12小时，用氯化铵水溶液淬灭反应。过滤，先后用水和乙醇清洗滤渣，烘干后，用氯苯重结晶。得白色晶体4g,产率：25％。(2)2,8-二氟-3,7-二溴-S,S-二氧-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000008
在100ml的三口圆底烧瓶，加入2,8-二氟-S,S-二氧-二苯并噻吩(3g，12mmol)和浓硫酸(50mL)，搅拌下分批加入NBS(5.3g，30mmol)。常温下避光反应24小时，反应完毕后将反应液缓慢倒入冰水中，有固体析出，抽滤，依次用碳酸氢钠水溶液、水和乙醇冲洗多次，烘干后，用邻二氯苯重结晶，得 白色晶体2g,产率40％。
实施例3：
3,7-二溴-2,8-二(3′-(N,N-二乙基胺基)丙氧基)-S,S-二氧-二苯并噻吩的制备路线:
(1)2,8-二溴-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000009
在1000毫升三口瓶中，加入二苯并噻吩(36.8g,200mmol)，铁粉(0.6g，10mmol)和氯仿(500mL)。搅拌至溶解，冰浴下滴加入溴(80g,500mmol),滴加完毕，室温下避光反应12小时，反应完毕后，向反应液中加入亚硫酸氢钠水溶液至溶液变白色，过滤，滤渣先后用水和甲醇冲洗几次，干燥后用四氢呋喃重结晶，得白色固体48g，产率：70％。
(2)2,8-二(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-二基)-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000010
在500毫升三口瓶中，加入2,8-二溴-二苯并噻吩(20.5g,30mmol)和无水四氢呋喃(THF)(300mL)。强力搅拌，将反应降温至-78℃,缓慢滴加正丁基锂溶液滴加入正丁基锂溶液(2.5M in THF,53mL,132mmol)，滴加完毕后，保持温度下反应2小时，一次性加入硼酸三甲酯(15.6g,150mmol)，让反应缓慢升至室温，再反应12小时，用氯化铵水溶液淬灭反应。旋转蒸发大部分溶液后，用二氯甲烷萃取，水洗3次，脱掉溶剂后进行柱层析，得白色晶体8.2g,产率：50％。
(3)2,8-二羟基-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000011
在150毫升三口瓶中，加入2,8-二(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-二基)-二苯并噻吩(8g,30mmol)和乙酸(60mL)。搅拌至溶解，加入双氧水(30mL)，温度下反应12小时。旋转蒸发大部分溶液后，用二氯甲烷萃取，水洗3次，脱掉溶剂后进行柱层析，得白色晶体5.6g,产率：90％。
(4)2,8-二(3′-溴丙氧基)-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000012
在100毫升三口瓶中，加入2,8-二羟基-二苯并噻吩(4.3g,20mmol)、碳酸钾(13.8g，100mmol)和1,3-二溴丙基(40.4g,200mmol)，100℃下反应12小时。反应完成后，将反应降至室温，将反应液倒至200mL水中，用二氯甲烷萃取，水洗3次，分离有机相，旋干，加压蒸馏掉过量的1,3-二溴丙基，粗产物进行柱层析，得无色油状液体8.2g,产率：90％。
(5)2,8-二(3′-溴丙氧基)-S,S-二氧-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000013
在100毫升三口瓶中，加入2,8-二(3′-溴丙氧基)-二苯并噻吩(7.3g,16mmol)、乙酸(40mmol)和双氧水(20mL)。回流反应2小时。反应完成后，旋走大部分乙酸，用二氯甲烷萃取，水洗3次，用甲醇重结晶得白色固体7.4g,产率：95％。
(6)3,7-二溴-2,8-二(3′-溴丙氧基)-S,S-二氧-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000014
在100毫升三口瓶中，加入2,8-二(3′-溴丙氧基)-S,S-二氧-二苯并噻吩(5.9g,12mmol)和液溴(4.8g,30mmoL)。室温下反应24小时。反应完成后，将反应液倒入水中，用二氯甲烷萃取，水洗3次，脱掉溶剂后进行柱层析，得白色固体3.9g,产率：50％。
(7)3,7-二溴-2,8-二(3′-(N,N-二乙基胺基)丙氧基)-S,S-二氧-二苯并噻吩的制备，反应式如下：
Figure PCTCN2014092731-appb-000015
氩气保护下，在50mL的两口瓶中，加入3,7-二溴-2,8-二(3′-溴丙氧基)-S,S-二氧-二苯并噻吩(3.2g,5mmol)和DMF(15mL)，搅拌下一次性加入二乙基胺(3.7g,50mmol)，回流下反应12小时。让反应降至室温，将反应混合物倒入 水中，并用二氯甲烷萃取，水洗3次，分离有机层，用无水MgSO4干燥，旋干溶剂后，用乙醇/四氢呋喃混合溶剂进行重结晶，得到白色固体2.8g，产率约90％。
(二)以下通过实施例对含S,S-二氧-二苯并噻吩的聚合物合成作进一步的说明，但本发明将不限于所列之例。
实施例4：
聚(4,9-二氢-4,4,9,9-四(4-己基苯基)-苯并二茚并[1,2-b:5,6-b’]-二噻吩-alt-3,7-(2,8-二氟-S,S-二氧-二苯并噻吩))(PIDT-SO)的制备，反应式如下：
Figure PCTCN2014092731-appb-000016
在50毫升两口瓶中，加入2,7-二(三甲基锡)-4,9-二氢-4,4,9,9-四(4-己基苯基)-苯并二茚并[1,2-b:5,6-b’]-二噻吩(0.616g，0.5mmol)、3,7-二溴-2,8-二氟-S,S-二氧-二苯并噻吩(0.174g,0.5mmol)、三(二亚苄基丙酮)二钯(0.006g)、三(2-甲苯基)膦(0.012g和甲苯(4mL)，180℃微波反应45分钟，结束反应，待反应降到室温后，将反应液沉析在甲醇中，先后用甲醇、丙酮进行索氏抽提，以氯仿为洗脱剂进行柱层析，干燥，得到橙色固体，产率：70％。1H NMR(300MHz,CDCl3)δ(ppm):8.01(s,ArH),7.50(s,ArH),7.38(s,ArH),7.23(s,ArH),7.20(s,ArH),7.13(s,ArH),7.11(s,ArH),2.59(m,CH2),1.61-1.59(m,CH2),1.31-1.27(m,CH2),0.88(t,CH3)。元素分析结果，计算值：C,78.85％；H,6.79％；S,8.31％。测试值：C,79.24％；H,6.41％；S,8.46％。
实施例5：
聚(4,9-二氢-4,4,9,9-四(4-己基苯基)-苯并二茚并[1,2-b:5,6-b’]-二噻吩-alt-3,7-二(4-己基噻吩-2-基)-S,S-二氧-二苯并噻吩)(PIDT-DHTSO)的制备，反应式如下：
Figure PCTCN2014092731-appb-000017
在50毫升两口瓶中，加入2,7-二(三甲基锡)-4,9-二氢-4,4,9,9-四(4-己基苯基)-苯并二茚并[1,2-b:5,6-b’]-二噻吩(0.616g，0.5mmol)、3,7-二(4-己基噻吩-2-溴)-S,S-二氧-二苯并噻吩(0.353g,0.5mmol)、三(二亚苄基丙酮)二钯(0.006g)、三(2-甲苯基)膦(0.012g)和甲苯(4mL)，180℃微波反应45分钟，结束反应，待反应降到室温后，将反应液沉析在甲醇中，先后用甲醇、丙酮进行索氏抽提，以氯仿为洗脱剂进行柱层析，干燥，得到橙红色固体，产率：75％。1H NMR(300MHz,CDCl3)δ(ppm)：7.76-7.74(m,ArH),7.47(s,ArH),7.23(s,ArH),7.20(s,ArH),7.13(s,ArH),7.11(s,ArH),2.79(s,CH2),2.59(m,CH2),1.61-1.56(m,CH2),1.32(m,CH2),0.88(t,CH3)。元素分析结果,计算值：C,79.29％；H,7.49％；S,11.02％。测试值：C,80.04％；H,7.71％；S,10.98％。
实施例6：
聚(4,8-二(2-乙基己基氧基)二噻吩并苯-co-3,7-S,S-二氧-二苯并噻吩-co-4,7-二(4-己基噻吩-2-基)-5,6-二辛氧基苯并[2,1,3]噻二唑)(PBDT-DHTOBPz)的制备,反应式如下：
Figure PCTCN2014092731-appb-000018
氩气保护下，在50毫升两口瓶中，加入2,6-二(三甲基锡)-4,8-(2-乙基己基氧基)-苯并[1,2-b；3,4-b]二噻吩(0.386g,0.5mmol)、3,7-二溴-S,S-二氧-二苯并噻吩(0.0174g,0.05mmol)、4,7-二(4-己基噻吩-2-溴)-5,6-二辛氧基苯并[2,1,3]噻二唑(0.321g,0.45mmol)、三(二亚苄基丙酮)二钯(0.006g)、三(2-甲苯基)膦(0.012g)和甲苯(15mL)，避光，加热100℃下反应72小时。第一次封端，加入2-三丁基锡噻吩(0.1g)，反应12小时后，第二次封端，加入2-溴噻吩(0.2g)，再反应12小时，结束反应，待反应降到室温后，将反应液沉析在甲醇中，先后用甲醇、丙酮进行索氏抽提，以氯苯为洗脱剂进行柱层析，干燥，得到褐色固体，产率：60％。1H NMR(300MHz,CDCl3)δ(ppm)：8.82(br,ArH),7.83(br,ArH),4.29(br,CH2),3.63(m,CH2),1.66(m,CH2),1.41-1.20(m,CH2),1.0(br, CH3)。元素分析结果,计算值：C,68.06％；H,7.45％；N,2.63％；S,15.62％。测试值：C,68.56％；H,7.82％；N,2.44％；S,15.88％。
实施例7：
聚(5,11-二(9-十七烷基)吲哚[3,2-b]咔唑-co-2,8-二(3′-(N,N-二乙基胺基)丙氧基)-3,7-S,S-二氧-二苯并噻吩-co-4,7-二(4-己基噻吩-2-基)-5,6-二辛氧基苯并[2,1,3]噻二唑)(PBDT-DHTOBPz)的制备，反应式如下：
Figure PCTCN2014092731-appb-000019
氩气保护下，在50毫升两口瓶中，加入3,9-二(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-二基)-5,11-二(9-十七烷基)吲哚[3,2-b]咔唑(0.493g,0.5mmol)、3,7-二溴-2,8-二(3′-(N,N-二乙基胺基)丙氧基)-S,S-二氧-二苯并噻吩(0.0632g,0.1mmol)、4,7-二(4-己基噻吩-2-溴)-5,6-二辛氧基苯并[2,1,3]噻二唑(0.286g,0.4mmol)、四(三苯基磷)钯(0.012g)和甲苯(15mL)，避光，加热90℃下反应72小时。第一次封端，加入苯硼酸(0.05g)，反应12小时后，第二次封端，加入溴苯(0.2g)，再反应12小时，结束反应，待反应降到室温后，将反应液沉析在甲醇中，用氯仿溶解后用去离子水洗三遍，浓缩有机相后沉析在甲醇中，干燥，得到暗红色固体，产率：70％。1H NMR(300MHz,CDCl3)δ(ppm):8.30(br,ArH),8.03-7.78(br,ArH),7.59-7.46(br,ArH),4.38(br,CH2),2.29-2.00(m,CH2,NCH2),1.78-1.16(m,NCH3,CH2),0.90-0.77(m,CH3)。元素分析结果,计算值：C,76.58％；H,9.28％；N,4.38％；S,7.00％。测试值：C,76.50％；H,9.03％；N,4.24％；S,7.12％。
对上述制备得到的产品进行热失重分析，其结果如图1所示，其中PBDT-DTOBT和PICz-DTOBT分别表示与PBDT-SO-DTOBT和PICz-SON-DTOBT对应的不含S,S-二氧-二苯并噻吩(SO)衍生物单元的聚合物， 聚合物的热分解温度均在300℃以上，能满足实际应用的需求。
上述制备得到的聚合物薄膜单位厚度的吸收光谱如图2所示，从图中可以看出含SO单元的聚合物比不含SO单元的聚合物具有较高的光吸收率，含2,8-二氟取代的SO单元的聚合物比同类型的聚合物有较高的光吸收率，这有利于相关的聚合物太阳电池器件短路电流的提高。
上述制备得到的聚合物电化学曲线的氧化过程如图3所示，其中含SO单元的聚合物比不含SO单元的聚合物具有较深的HOMO能级，含2,8-二氟取代的SO单元的聚合物比同类型的聚合物有较深的HOMO能级，这有利于相关的聚合物太阳电池器件开路电压的提高。
表1.聚合物基本物理性能
Figure PCTCN2014092731-appb-000020
表1中，a凝胶渗透色谱测定；b电化学方法测定；bHOMO能级与光学带隙计算得到；c由薄膜吸收边计算；d由薄膜吸收计算；e每纳米薄膜在最大吸收波长处的吸光率；f由有机场效应晶体管(器件结构：Si/SiO2/OTS/polymer/Ag)测出；g由空间电荷限制电流(SCLC)方法测出。
表1为相关聚合物的物理性质。从表1可见，聚合物均具有较高的数均分子量和较小的分子量分散系数。含SO单元的聚合物比不含SO单元的聚合物具有相对较低的HOMO能级、较高的吸光率和空穴迁移率。以其作为电子给体材料，有利于提高太阳电池器件的开路电压和短路电流；以其作为活性层，有利于提高有机场效应晶体管的空穴迁移率。
(三)以下的示例对本发明所提出的电子给体聚合物所制作器件与特性之说明，但本发明将不限于所列之例。
实施例8：
聚合物太阳电池器件的制备和性能
ITO玻璃经过超声波清洗后，用氧等离子体处理，ITO玻璃的方块电阻为10Ω/□，在ITO上旋涂一层界面层PFN，将以上所合成的聚合物与PC61BM(或PC71BM)分别配制成溶液后进行混合，旋涂在PFN层上形成活性层，在活性层上蒸镀上一层MoO3，最后蒸镀上Al金属电极。在AM 1.5模拟太阳光的照射下测量其电池特性。
以上所述的ITO为氧化铟锡导电玻璃；PC61BM为英文“methanofullerene[6,6]-phenyl C61-butyric acid methyl ester”之简称,PFN为聚[9,9-二辛基芴-9,9-双(N,N-二甲基胺丙基)芴]。
上述制备得到的聚合物太阳电池的电流-电压曲线如图4所示，可以看出含SO单元的聚合物普遍具有较高的开路电压，且相对于不含SO单元的聚合物来说，前者具有更好的光电响应特性。含2,8-二氟取代的SO单元的聚合物比同类型的聚合物具有较高的开路电压，含侧链极性基团取代SO单元的聚合物比同类型的不含该单元的聚合物同时具有较高的短路电流和开路电压，具有一定的界面修饰特性。
在聚合物PBDT-DTOBT:PC71BM和PBDT-SO-DTOBT:PC71BM薄膜的AFM高度图和相图分别见图5(a,b)及(c,d))。PIDT-DTOBT:PC71BM和PIDT-SO-DTOBT:PC71BM薄膜的表面粗糙度分别为1.235nm和0.773nm，其中基于含SO单元聚合物共混薄膜比基于不含SO单元的聚合物共混薄膜有更均匀的相分离，有利于增加本体异质结的有效面积，从而提高相关器件的光电性能。
表2为聚合物太阳电池的光伏特性，其中含SO单元的聚合物比同类型不含SO单元的聚合物在同类型器件中表现出相对较高的开路电压、短路电流、填充因子及光电转换效率。此外，聚合物PIDT-DHTSO的光电转换效率是目前报道的带隙超过2.2eV的最高值。
表2.聚合物光伏性能(AM 1.5,100mW/cm2)
Figure PCTCN2014092731-appb-000021
a器件结构：ITO/PFN/polymer:PC61BM(1:3,w/w)/MoO3/Al；
b器件结构：ITO/PFN/polymer:PC71BM(1:3,w/w)/MoO3/Al；
c器件结构：ITO/ZnO/PFN/polymer:PC71BM(1:2,w/w)/MoO3/Al；
d器件结构：ITO/PEDOT/polymer:PC71BM(1:3,w/w)/Al。
实施例9：
有机场效应晶体管器件的制备和性能
有机场效应二极管(OFET)采用顶接触结构，用银做原电极和漏电极。用高n-型参杂硅和热生长的氧化硅(300nm)分别作为底栅极和栅极电介质层。辛基三氯硅烷(OTS)作为栅极电介质层的界面材料。聚合物膜(80nm)旋涂在OTS层上，然后在120℃进行退火10min处理。银电极层(60nm)用真空蒸镀的方法镀在聚合物薄上。OFET器件结构为：Si/SiO2/OTS/聚合物/Ag，器件长宽比为60:1。OFET器件性能测试是在Aglient 4155C平台上在大气环境下进行的。
聚合物PIDT-FSO和PIDT-DHTSO的有机场效应晶体管的输出(a,c)和转移(b,d)特征曲线如图6所示。从特征曲线可以得到含SO的聚合物在有机场效应晶体管中表现出良好的电场响应特性，计算得的空穴迁移率均在1×10-4以上。

Claims (3)

  1. 含S,S-二氧-二苯并噻吩单元的电子给体聚合物，其特征在于，具有如下化学结式：
    Figure PCTCN2014092731-appb-100001
    其中：x、y为摩尔分数，0<x≤1，0≤y<1，x+y＝1；R为H、F、烷氧基或末端含极性基团的烷氧基链；所述末端含极性基团包括胺基、磷酸酯基或氰基；D单元具有如下化学结构中的一种以上：
    Figure PCTCN2014092731-appb-100002
    其中，R1、R2为氢、1～30个碳原子数的烷基、或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、硝基、苯基、噻吩基取代，或氢原子被卤素原子取代；A单元具有如下化学结构中的一种以上：
    Figure PCTCN2014092731-appb-100003
    其中，X1、X2为N、O、S或Se，X3为H或F，R3、R4为氢、氟或1～30个碳原子数的烷氧基链，R5为1～30个碳原子数的烷基链或烷苯基链。
  2. 根据权利要求1所述的含S,S-二氧-二苯并噻吩单元的电子给体聚合物，其特征在于，聚合度n为1～300。
  3. 权利要求1所述的含S,S-二氧-二苯并噻吩单元的电子给体聚合物应用于有机太阳电池或有机场效应管器件中。
PCT/CN2014/092731 2014-05-07 2014-12-02 含s,s-二氧-二苯并噻吩单元的电子给体聚合物及其应用 Ceased WO2015169083A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410190315.7A CN104004165B (zh) 2014-05-07 2014-05-07 含s,s-二氧-二苯并噻吩单元的电子给体聚合物及其应用
CN201410190315.7 2014-05-07

Publications (1)

Publication Number Publication Date
WO2015169083A1 true WO2015169083A1 (zh) 2015-11-12

Family

ID=51365089

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/092731 Ceased WO2015169083A1 (zh) 2014-05-07 2014-12-02 含s,s-二氧-二苯并噻吩单元的电子给体聚合物及其应用

Country Status (2)

Country Link
CN (1) CN104004165B (zh)
WO (1) WO2015169083A1 (zh)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104004165B (zh) * 2014-05-07 2016-08-24 华南理工大学 含s,s-二氧-二苯并噻吩单元的电子给体聚合物及其应用
CN109891615B (zh) * 2016-10-11 2023-11-17 香港科技大学 基于一种供体聚合物和两种受体的三元混合物有机太阳能电池
CN106832228A (zh) * 2016-11-11 2017-06-13 华南理工大学 一种分子链末端修饰含有s,s‑二氧‑二苯噻吩的共聚物发光材料及其制备方法与应用
CN106633002B (zh) * 2016-12-09 2020-06-19 华南理工大学 三芳胺端基含量可调的主链含s,s-二氧-二苯并噻吩的聚合物及其制备方法与应用
CN106633004A (zh) * 2017-01-04 2017-05-10 华南理工大学 一种基于萘并硫氧芴单元的共轭聚合物及其制备方法与应用
CN106928435B (zh) * 2017-03-23 2020-09-22 华南理工大学 一种含氟代侧基的共聚物发光材料及其制备方法与应用
CN107759774B (zh) * 2017-10-23 2020-03-24 华南协同创新研究院 主链含s,s-二氧-二苯并噻吩的d-a型聚合物及其制备方法与应用
CN110776622A (zh) * 2018-07-31 2020-02-11 华南理工大学 含s,s-二氧-二苯并噻吩衍生物单元的聚合物及其制备方法与应用
CN110776620B (zh) * 2018-07-31 2022-02-15 华南理工大学 含S,S-二氧-二苯并噻吩衍生物单元的D-π-A聚合物及其制备方法与应用
CN109337046B (zh) * 2018-09-11 2024-03-15 常州大学 含二苯并噻吩亚砜单元的聚合物给体材料及其制备

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1528804A (zh) * 2003-09-29 2004-09-15 上海交通大学 含二苯并二氧化噻吩基团的聚合物及其制备方法
WO2007132236A1 (en) * 2006-05-16 2007-11-22 University Of Durham Novel light emitting polymeric compositions and uses thereof
CN101712674A (zh) * 2009-11-13 2010-05-26 华南理工大学 烷基取代-s,s-二氧-二苯并噻吩单体及其制备方法与聚合物
WO2012087243A1 (en) * 2010-12-20 2012-06-28 Agency For Science, Technology And Research New p-type low bandgap polymers and their use
CN102850528A (zh) * 2012-05-29 2013-01-02 华南理工大学 含s,s-二氧-二苯并噻吩单元的发光聚合物及其应用
EP2554626A2 (en) * 2009-09-18 2013-02-06 Thorn Lighting Ltd Electroluminescent materials and devices
CN103224486A (zh) * 2013-04-03 2013-07-31 华南理工大学 含极性取代基团s,s-二氧-二苯并噻吩单体及其水/醇溶性聚合物与应用
CN104004165A (zh) * 2014-05-07 2014-08-27 华南理工大学 含s,s-二氧-二苯并噻吩单元的电子给体聚合物及其应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103382248A (zh) * 2012-05-04 2013-11-06 海洋王照明科技股份有限公司 二氧硫芴基共聚物、其制备方法以及聚合物发光二极管

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1528804A (zh) * 2003-09-29 2004-09-15 上海交通大学 含二苯并二氧化噻吩基团的聚合物及其制备方法
WO2007132236A1 (en) * 2006-05-16 2007-11-22 University Of Durham Novel light emitting polymeric compositions and uses thereof
EP2554626A2 (en) * 2009-09-18 2013-02-06 Thorn Lighting Ltd Electroluminescent materials and devices
CN101712674A (zh) * 2009-11-13 2010-05-26 华南理工大学 烷基取代-s,s-二氧-二苯并噻吩单体及其制备方法与聚合物
WO2012087243A1 (en) * 2010-12-20 2012-06-28 Agency For Science, Technology And Research New p-type low bandgap polymers and their use
CN102850528A (zh) * 2012-05-29 2013-01-02 华南理工大学 含s,s-二氧-二苯并噻吩单元的发光聚合物及其应用
CN103224486A (zh) * 2013-04-03 2013-07-31 华南理工大学 含极性取代基团s,s-二氧-二苯并噻吩单体及其水/醇溶性聚合物与应用
CN104004165A (zh) * 2014-05-07 2014-08-27 华南理工大学 含s,s-二氧-二苯并噻吩单元的电子给体聚合物及其应用

Also Published As

Publication number Publication date
CN104004165A (zh) 2014-08-27
CN104004165B (zh) 2016-08-24

Similar Documents

Publication Publication Date Title
CN104004165B (zh) 含s,s-二氧-二苯并噻吩单元的电子给体聚合物及其应用
CN102482421B (zh) 用于聚合物太阳能电池活性层材料的具有羰基取代噻吩并[3，4-b]噻吩单元的共轭聚合物
JP5935229B2 (ja) 重合体およびこれを含む有機太陽電池
CN103804271B (zh) 含有吸电子基团的异靛青类化合物及其制备和应用
CN104177378A (zh) 四取代的苝二酰亚胺二聚体、其制备方法及其在有机光伏器件中的应用
Ye et al. Dithienosilole-bridged small molecules with different alkyl group substituents for organic solar cells exhibiting high open-circuit voltage
Zhou et al. Enhancing the photovoltaic performance of triphenylamine based star-shaped molecules by tuning the moiety sequence of their arms in organic solar cells
Deng et al. Triphenylamine-containing linear DAD molecules with benzothiadiazole as acceptor unit for bulk-heterojunction organic solar cells
CN102858841A (zh) 含稠环噻吩单元喹喔啉共轭聚合物及其制备方法和应用
Zhang et al. Solution processable donor–acceptor oligothiophenes for bulk-heterojunction solar cells
Ong et al. Design and synthesis of benzothiadiazole–oligothiophene polymers for organic solar cell applications
Cai et al. Effects of including electron-withdrawing atoms on the physical and photovoltaic properties of indacenodithieno [3, 2-b] thiophene-based donor–acceptor polymers: towards an acceptor design for efficient polymer solar cells
CN103059271A (zh) 含5，10-二酮-4，9-二氮杂芘共轭聚合物及制备
CN107383080A (zh) 一种不对称卟啉有机小分子光伏材料及其制备方法与应用
Ashraf et al. Fused ring thiophene-based poly (heteroarylene ethynylene) s for organic solar cells
Yang et al. Star-shaped chromophores based on a benzodithiophene fused truxene core for solution processed organic solar cells
EP2927259B1 (en) Benzodithiophene based copolymer containing thiophene pyrroledione units and preparing method and applications thereof
CN103319695B (zh) 含4,9-二氮杂芘的共轭聚合物及其制备方法与应用
CN102753599B (zh) 芴类共聚物、其制备方法及其应用
KR102093470B1 (ko) 신규한 화합물 및 이를 이용하는 유기 전자 소자
CN102898626B (zh) 含萘并[1,2-c:5,6-c]二(2-烷基-[1,2,3]三唑)的有机半导体材料及其应用
Tu et al. Ladder-type heteroheptacene-cored semiconductors for small-molecule solar cells
Kim et al. 2, 2-dimethyl-2 H-benzimidazole based small molecules for organic solar cells
Li et al. Synthesis and photovoltaic performances of conjugated copolymers with 4, 7-dithien-5-yl-2, 1, 3-benzothiadiazole and di (p-tolyl) phenylamine side groups
KR101183528B1 (ko) 반도체성 유기 고분자 재료 및 이를 포함하는 광기전력 소자

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14891543

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14891543

Country of ref document: EP

Kind code of ref document: A1