WO2015169083A1 - Polymère donneur d'électrons contenant un motif s,s-dioxo-dibenzothiophène et son utilisation - Google Patents

Polymère donneur d'électrons contenant un motif s,s-dioxo-dibenzothiophène et son utilisation Download PDF

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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
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group
polymer
dibenzothiophene
dioxy
electron donor
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PCT/CN2014/092731
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Chinese (zh)
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杨伟
何锐锋
徐进
张斌
吴宏滨
曹镛
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华南理工大学
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    • 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

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  • 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 .

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  • 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

L'invention concerne un polymère donneur d'électrons contenant un motif S,S-dioxo-dibenzothiophène et son utilisation. La chaîne principale du polymère donneur d'électrons contient un motif S,S-dioxo-dibenzothiophène. Par un procédé de polymérisation, tel que le procédé de Stille, le procédé de Suzuki, etc., un nouveau polymère conjugué à structure D-A est formé. Le motif S,S-dioxo-dibenzothiophène a une bonne planéité et une électronégativité élevée. Le polymère est doté de propriétés, telles qu'un niveau d'énergie d'HOMO relativement bas, une forte interaction intermoléculaire, un coefficient d'absorption de la lumière élevé, une mobilité élevée et une réponse photoélectrique relativement élevée, de sorte que le matériau polymère correspondant a de larges perspectives d'application dans des cellules solaires organiques ou des dispositifs à transistor à effet de champ organique.
PCT/CN2014/092731 2014-05-07 2014-12-02 Polymère donneur d'électrons contenant un motif s,s-dioxo-dibenzothiophène et son utilisation WO2015169083A1 (fr)

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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
US20190229269A1 (en) * 2016-10-11 2019-07-25 The Hong Kong University Of Science And Technology Ternary blend organic solar cells based on one donor polymer and two acceptors
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
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
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
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 (fr) * 2006-05-16 2007-11-22 University Of Durham Nouvelles compositions polymÈres Électroluminescentes et leurs utilisations
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 (fr) * 2010-12-20 2012-06-28 Agency For Science, Technology And Research Nouveaux polymères à faible largeur de bande interdite de type p et leur utilisation
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 (fr) * 2009-09-18 2013-02-06 Thorn Lighting Ltd Matières électroluminescentes et dispositifs correspondants
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 (fr) * 2006-05-16 2007-11-22 University Of Durham Nouvelles compositions polymÈres Électroluminescentes et leurs utilisations
EP2554626A2 (fr) * 2009-09-18 2013-02-06 Thorn Lighting Ltd Matières électroluminescentes et dispositifs correspondants
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 (fr) * 2010-12-20 2012-06-28 Agency For Science, Technology And Research Nouveaux polymères à faible largeur de bande interdite de type p et leur utilisation
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

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