WO2012034264A1 - 含芴有机半导体材料,其制备方法和应用 - Google Patents

含芴有机半导体材料,其制备方法和应用 Download PDF

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WO2012034264A1
WO2012034264A1 PCT/CN2010/076838 CN2010076838W WO2012034264A1 WO 2012034264 A1 WO2012034264 A1 WO 2012034264A1 CN 2010076838 W CN2010076838 W CN 2010076838W WO 2012034264 A1 WO2012034264 A1 WO 2012034264A1
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organic semiconductor
semiconductor material
organic
tetradecyl
containing organic
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PCT/CN2010/076838
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English (en)
French (fr)
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周明杰
黄杰
黄佳乐
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海洋王照明科技股份有限公司
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Priority to CN201080068946.1A priority Critical patent/CN103080183B/zh
Priority to EP10857120.9A priority patent/EP2617754A4/en
Priority to US13/821,657 priority patent/US20130172508A1/en
Priority to PCT/CN2010/076838 priority patent/WO2012034264A1/zh
Priority to JP2013527439A priority patent/JP5665993B2/ja
Publication of WO2012034264A1 publication Critical patent/WO2012034264A1/zh

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Definitions

  • the present invention relates to a copolymer organic semiconductor material, and more particularly to a class of germanium-containing organic semiconductor materials.
  • the invention also relates to a process for the preparation of a class of germanium-containing organic semiconductor materials and their use.
  • High-efficiency solar cells are usually made of inorganic semiconductors.
  • the main silicon-crystalline solar cells on the market today have complicated production processes, serious pollution, high energy consumption and high cost, which inhibits the development of commercial applications. Therefore, the use of inexpensive materials to prepare low-cost, high-efficiency solar cells has always been a research hotspot and a difficult point in the field of photovoltaics.
  • organic semiconductor materials have good environmental stability, low preparation cost, easy function modulation, flexibility and film formation.
  • due to the relatively simple processing of organic solar cells low temperature operation, devices The cost of production is also low, which has attracted much attention and become a cheap and attractive solar cell material.
  • the potential advantages of organic solar cells include: large-area manufacturing, flexible substrates, environmental friendliness, and ease of use.
  • organic solar cells have developed rapidly, they are still much less efficient than inorganic solar cells.
  • the main constraints limiting their performance are: relatively low carrier mobility of organic semiconductor devices, spectrum of devices. The response does not match the solar radiation spectrum, the red region of the high photon flux is not effectively utilized, and the electrode collection efficiency of the carriers is low.
  • developing new materials and greatly improving their energy conversion efficiency are still the primary tasks in this research field.
  • the structure is relatively rigid, so it is chemically stable; and other branches can be introduced at the 9 position by chemical reaction. 2, 7 positions are easy to carry out cross-coupling of transition metals, so it has good chemical properties. Modification; In addition, it has a relatively wide band gap and a low HOMO level, excellent quantum efficiency, hole transport properties and film formation, so ruthenium and its derivatives are widely used in the study of photovoltaic materials. Bismuth and its derivatives have good stability and good film formation; its UV-visible spectrum exhibits wide finger peak absorption, which is beneficial to improve the absorption coverage of sunlight; and it has suitable current carrying capacity.
  • the sub-transmission characteristics, the crystal mobility of the crystal at room temperature up to 3 cm 2 /Vs, is a rare class of organic organic photovoltaic materials, but it has rarely been reported, which greatly limits its application range.
  • the thieno[3,4-c]pyrrole-4,6-dione has a simple structure, a relatively compact atomic position in the molecule, and a symmetrical structure.
  • a conjugated polymer unit of a ruthenium-containing organic semiconductor material Very strong electron absorption.
  • the solubility and processability of the conjugated polymer of the ruthenium-containing organic semiconductor material can also be well increased by adding an alkane chain to the pyrrole ring. At present, it has broad application prospects in the field of organic optoelectronics research.
  • a class of germanium-containing semiconductor materials according to the present invention has the following general formula (P):
  • R 2 may be the same or different, independently of each other, a mono- or poly-substituted functional group selected from a straight or branched alkyl group or alkoxy group selected from the group consisting of a hydrogen atom, a fluorine atom, a cyano group, and a d-Cu group.
  • a aryl group, an aryl group, or a heteroaryl group preferably, R 2 is a linear or branched alkyl group or alkoxy group having d ⁇ C 18 ;
  • R 3 is a hydrogen atom or an alkyl group of ( ⁇ 2( ); preferably, R 3 is an alkyl group of d to C 12 .
  • a type of ruthenium-containing organic semiconductor material designed by the present invention is prepared as follows:
  • Step 1 Under anhydrous and anaerobic conditions, 2,7-dibromo-9,9-dialkylfluorene and n-butyllithium (n-BuLi, the same as below) or tert-butyllithium (t-BuLi) At -70 ° C ⁇ -85 ° C in a molar ratio of 1: 2 ⁇ 4 into the second solvent, and then added 2-isopropoxy-4, 4, 5, 5-tetradecyl-1 , 3,2-dioxaborolane or dipinacol diboron, condensation reaction for 12 to 48 hours, to obtain the product, ie 2, 7-bis( 4, 4, 5, 5-tetradecyl- 1,3,2-dioxaborolanyl)-9,9-dialkylanthracene; wherein the second solvent is at least tetrahydrofuran, diethyl ether, dichlorodecane, trichlorodecane or ethyl acetate a m
  • Step 2 In an anaerobic environment, the structural formula is 2,7-two (4,4
  • the ruthenium-containing organic semiconductor material wherein the catalyst is Pd(PPh 3 ) 4 , Pd(OAc) 2 , tricyclohexylphosphine, Pd 2 (dba) 3 /P(o-Tol) 3 or Pd (PPh 3 2 Cl 2 ; lye is NaOH aqueous solution, Na 2 CO 3 aqueous solution, NaHC0 3 aqueous solution or tetraethylammonium hydroxide aqueous solution, the first solvent is toluene, ethylene glycol dioxime ether, tetrahydrofuran, diethyl ether, dichloroanthracene Alkane, trichlorodecane or ethyl acetate, etc., the amount of the catalyst is 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan)-9 , the molar amount of 9-dialkylhydrazine is 0.0
  • the ruthenium and 1,3-bis(5-bromothienyl)-thieno[3,4-c]pyrrole-4,6-dione group are introduced into the molecule of the organic semiconductor material of the invention, which is obviously improved. Its carrier migration performance and light absorption range;
  • the organic semiconductor material of the present invention contains a ruthenium unit, which has improved carrier mobility and 1,3-bis(5-bromothienyl)-
  • the 5-position on the thieno[3,4-c]pyrrole-4,6-dione introduces an alkyl group and the like to improve the solubility thereof, thereby improving the processability;
  • 1,3-bis(5-bromothienyl)-thieno[3,4-c]pyrrole-4,6-dione has a simple structure, a relatively compact atomic position in the molecule, and a structural symmetry.
  • Conjugated polymer as a ruthenium-containing organic semiconductor material When the unit is used, it has a strong electron absorption effect.
  • the 1,3-bis(5-bromothienyl)-thieno[3,4-c]pyrrole-4,6-dione unit and the fluorene unit are copolymerized with the fluorene unit to effectively adjust the band gap of the organic semiconductor material.
  • the absorption band is pushed to the infrared and near-infrared regions, so that the absorbance is strong, the light absorption range is wide, the utilization of sunlight is improved, and the organic semiconductor material is excellent in solubility and charge transport performance. ;
  • the preparation method of the organic semiconductor material is simple in process, high in yield, mild in reaction condition, easy to operate and control, and suitable for industrial production.
  • the invention provides a class of germanium-containing organic semiconductor materials having the following general formula (P):
  • n is an integer between 1 and 100; m is an integer from 1 to 20; preferably m ranges from 6 to 12
  • R 2 may be the same or different, and independently represent a mono- or poly-substituted functional group, a linear or branched alkyl or alkoxy group, an aryl group or a heteroaryl group selected from a hydrogen atom, a fluorine atom, a cyano group, d-Cu); preferably, R 2 is a group having d ⁇ C 18 a linear or branched alkyl or alkoxy group;
  • R 3 is a hydrogen atom or an alkyl group of ( ⁇ 2 2 ); preferably, R 3 is an alkyl group of d to C 12 .
  • a class of germanium-containing organic semiconductor materials the preparation scheme of which is as follows:
  • Step S1 2,7-dibromo-9,9-dialkylfluorene and n-butyllithium at a molar ratio of 1:2 ⁇ at -70 ° C to -85 ° C under anhydrous anoxic reaction conditions 4 is added to the second solvent, and then 2-isopropoxy-4,4,5,5-tetradecyl-1,3,2-dioxaborolane or dipinacol diboron ( The molar amount is 2 to 4 times that of 2,7-dibromo-9,9-dialkylfluorene, and the reaction is carried out for 12 to 48 hours to obtain a product, that is, 2, 7-bis (4, 4, 5, 5- Tetradecyl-1,3,2-dioxaborolanyl)-9,9-dialkylfluorene; wherein the second solvent is tetrahydrofuran, diethyl ether, dichlorodecane, trichlorodecane or acetic acid At least one of the esters has
  • Step S2 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolanyl)-9,9-dialkyl in an anaerobic environment Ruthenium, 9,10-dibromoindole or a derivative thereof, 1,3-bis(5-bromothienyl)-thieno[3,4-c]pyrrole-4,6-dione or a derivative thereof
  • Ratio i: j: k mixed, and satisfies i j+k, i, j, k is a positive real number
  • Suzuki reaction is carried out at 70 ⁇ : 100 °C, catalyst, lye and first solvent for 24-72 hours.
  • the catalyst is Pd(PPh 3 ) 4 , Pd(OAc) 2 , tricyclohexylphosphine, Pd 2 (dba) 3 /P(o-Tol) 3 or Pd (PPh 3 2 Cl 2 ; lye is NaOH aqueous solution, Na 2 CO 3 aqueous solution, NaHC0 3 aqueous solution or tetraethylammonium hydroxide aqueous solution, the first solvent is toluene, ethylene glycol dioxime ether, tetrahydrofuran, diethyl ether, dichloroanthracene Alkane, trichlorodecane or ethyl acetate, etc., the amount of the catalyst is 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan)-9 , the molar amount of 9-
  • the oxygen-free environment of the present invention is composed of a mixture of nitrogen (N 2 ) and/or an inert gas.
  • the present invention develops an organic semiconductor material containing ruthenium and applies it to fields such as organic solar cells.
  • the material has a lower energy gap, a higher mobility, a wider absorption range of the spectrum, and this material facilitates the more efficient transport of carriers within the active layer material.
  • the organic solar cell prepared by using the material of the invention as an active material can effectively increase the order and regularity of alignment between groups and molecular segments in the molecule after high temperature annealing, and improve the transport of carrier mobility. Speed and efficiency, which in turn increases the efficiency of photoelectric conversion.
  • This embodiment discloses the bismuth-containing organic semiconductor material polymers P1 and P2 having the following structure:
  • Step 1 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan)--9,9-dioctylfluorene: Set up a water-free anaerobic reactor, add 2.8 mmol of white 2,7-dibromo-9,9-dioctyl hydrazine to a three-neck bottle under constant stirring and N 2 protection, and inject 150 ml of refined with a syringe. The tetrahydrofuran solvent was slowly injected into 27.0 mmol of n-BuLi by a syringe at -78 ° C, and the reaction was stirred for 2 hours.
  • the ruthenium-containing organic semiconductor material polymer/chloroform solution was steamed to Remaining About 5 ml, it was dropped into a methanol solvent and stirred for several hours, and finally, the cerium-containing organic semiconductor material polymer P1 was collected and dried.
  • the ruthenium-containing organic semiconductor material polymer is extracted by a Soxhlet extractor to increase the monodispersity of the molecular weight of the ruthenium-containing organic semiconductor material polymer.
  • the purified cerium-containing organic semiconductor material polymer P1 is dissolved in purified tetrahydrofuran to form a 1 mg/lmL solution, and the insoluble matter is filtered off with an instrument-specific filter membrane to a volume of 10 ⁇ l.
  • the injection speed of lml/min was tested by GPC, and the number average molecular weight was Mn 69000.
  • the monodispersity of the polymer containing ruthenium-containing organic semiconductor material was 1.31 and n was 100.
  • the amount, the injection speed of lml/min was subjected to GPC test, and the number average molecular weight was Mn 41200.
  • the monodispersity of the polymer containing ruthenium-containing organic semiconductor material was 1.46, and n was 65.
  • Step 1 Preparation of 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan)-yl-9,9-dihexyl fluorene: preparation process thereof Referring to step 1 in the first embodiment, only the argon gas is used to construct the anaerobic environmental protection gas. Steps 3, P3, and P4 are prepared:
  • the alcohol solvent was stirred for several hours, and finally the ruthenium-containing organic semiconductor material polymer P3 was collected and dried.
  • the ruthenium-containing organic semiconductor material polymer is extracted by a Soxhlet extractor to increase the monodispersity of the molecular weight of the ruthenium-containing organic semiconductor material polymer.
  • the amount, the injection speed of lml/min was subjected to GPC test, and the number average molecular weight was Mn 31500.
  • the monodispersity of the polymer containing ruthenium-containing organic semiconductor material was 2.03, and n was 43.
  • This embodiment discloses the following organic semiconductor material-containing polymers P5 and P6 having the following structure:
  • Step 1 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolanyl)-9,9-di(dodecyl)fluorene :
  • the preparation process is as described in the first step of the embodiment 1, except that a mixture of nitrogen and argon is used to construct an oxygen-free atmosphere.
  • the sterol solvent was stirred for several hours, and finally the cerium-containing organic semiconductor material polymer P5 was collected and dried.
  • the ruthenium-containing organic semiconductor material polymer is extracted by a Soxhlet extractor to increase the monodispersity of the molecular weight of the ruthenium-containing organic semiconductor material polymer.
  • the purified cerium-containing organic semiconductor material polymer P5 is dissolved in purified tetrahydrofuran to form a 1 mg/lmL solution, and the insoluble matter is filtered off with a special filter membrane.
  • the GPC test was carried out at a sampling rate of 10 ⁇ l and a throughput of 1 ml/min, and the number average molecular weight was Mn 20300.
  • the monodispersity of the polymer containing the ruthenium-containing organic semiconductor material was 2.33 and n was 25.
  • This embodiment discloses the following organic semiconductor material-containing polymers P7 and P8 having the following structure:
  • Step 1 Preparation of 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan)yl-9,9-diindenylfluorene: preparation process thereof Refer to step one in Example 1.
  • the ruthenium-containing organic semiconductor material polymer/chloroform solution was steamed to about 5 ml, and the mixture was dropped into decyl alcohol. The solvent was stirred for several hours, and finally the ruthenium-containing organic semiconductor material polymer P7 was collected and dried.
  • the ruthenium-containing organic semiconductor material polymer is extracted by a Soxhlet extractor to increase the monodispersity of the molecular weight of the ruthenium-containing organic semiconductor material polymer.
  • the purified ruthenium-containing organic semiconductor material polymer P7 is dissolved in purified tetrahydrofuran to form a 1 mg/lmL solution, and the insoluble matter is filtered off with an instrument-specific filter membrane.
  • the GPC test was carried out at a sampling rate of 10 ⁇ l and a throughput of 1 ml/min, and the number average molecular weight was Mn 56700.
  • the monodispersity of the polymer containing the ruthenium-containing organic semiconductor material was 1.43 and n was 73.
  • the purified cerium-containing organic semiconductor material polymer P8 is dissolved in purified tetrahydrofuran to form a 1 mg/lmL solution, and the insoluble matter is filtered off with an instrument-specific filter membrane to 10 ⁇ l.
  • the injection rate of lml/min was measured by GPC, and the number average molecular weight was Mn 47700.
  • the monodispersity of the polymer containing ruthenium-containing organic semiconductor material was 1.31 and n was 60.
  • This embodiment discloses a polymer of germanium-containing organic semiconductor materials P9 and P10 having the following structure:
  • Step 1 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan)--9,9-dioctylfluorene: Preparation Process Refer to step one in Example 1.
  • the mixture was dropped into a methanol solvent and stirred for several hours, and finally the ruthenium-containing organic semiconductor material polymer P9 was collected and dried.
  • the ruthenium-containing organic semiconductor material polymer is extracted by a Soxhlet extractor to increase the monodispersity of the molecular weight of the ruthenium-containing organic semiconductor material polymer.
  • the purified ruthenium-containing organic semiconductor material polymer P9 is dissolved in purified tetrahydrofuran to form a 1 mg/lmL solution, and the insoluble matter is filtered off with an instrument-specific filter membrane to a volume of 10 ⁇ l. , lml/min injection speed for GPC test, number average molecular weight Mn 30000, including
  • the organic semiconductor material has a monodispersity of 1.83 and n of 33.
  • the purified cerium-containing organic semiconductor material polymer P10 is dissolved in purified tetrahydrofuran to form a 1 mg/lmL solution, and the insoluble matter is filtered off with an instrument-specific filter membrane to 10 ⁇ l.
  • the amount, the injection speed of lml/min was subjected to GPC test, and the number average molecular weight was Mn 26400.
  • the monodispersity of the polymer containing ruthenium-containing organic semiconductor material was 2.01, and n was 30.
  • the invention also provides the structural formula as
  • Polymer solar cells organic electroluminescence, organic field effect transistors, organic optical storage, organic nonlinear devices and organic laser devices.
  • the following examples are the use of a class of germanium-containing organic semiconductor materials in organic solar cells, organic field effect transistors, and organic electroluminescent devices.
  • the substrate ⁇ in the present embodiment is made of ITO glass, glass is used as a substrate substrate, and ITO is used as a conductive layer.
  • the structure of the organic solar cell device is: glass 11 / ITO layer 12 / PEDOT: PSS layer 13 / active layer 14 / A1 layer 15; wherein the active layer is made of a mixture, including an electron donor material, PCBM It is an electron acceptor material; the electron donor material is made of P1 in the first embodiment, and the electron acceptor material is [6,6] phenyl-C 61 -butyrate butyrate (PCBM); ITO is a sheet resistance 10-20 ⁇ / ⁇ of indium tin oxide, PEDOT is poly(3,4-ethylenedioxythiophene), PSS is poly(styrenesulfonic acid); ITO having a sheet resistance of 18 ⁇ / ⁇ is preferred.
  • the preparation process of the organic solar cell device is:
  • ITO indium tin oxide
  • a layer of modified PEDOT:PSS layer 13 is applied on the surface of the ITO, and the thickness is 20-300 nm;
  • an active layer 14 to a poly(3,4-ethylenedioxythiophene): PSS poly(styrenesulfonic acid) layer by spin coating, having a thickness of 50-300 nm, the active layer a mixture of P1 and [6,6]phenyl-C 61 -butyrate (PCBM ) in the first embodiment;
  • PSS poly(styrenesulfonic acid) layer by spin coating, having a thickness of 50-300 nm, the active layer a mixture of P1 and [6,6]phenyl-C 61 -butyrate (PCBM ) in the first embodiment;
  • Metal aluminum is vacuum-deposited on the surface of the active layer to form a metal aluminum layer 15 as a cathode, and an organic solar cell device is obtained;
  • the organic solar cell device was encapsulated with epoxy resin, annealed at 110 ° C for 1.5 hours, and then cooled to room temperature. Since the chemical structure of the material is more regular and ordered after annealing, the carrier transmission speed and efficiency are improved, thereby improving the photoelectric conversion efficiency of the device.
  • the thickness of the ITO, PEDOT:PSS layer, active layer, and A1 layer are 150 nm, 50 nm, 120 nm, and 100 nm, respectively.
  • An organic electroluminescent device having a structure as shown in Fig. 2; in the embodiment, the substrate is made of ITO glass, glass is used as a substrate substrate, and ITO is used as a conductive layer.
  • the structure of the organic electroluminescent device is: glass 21 / ITO layer 22 / light-emitting layer 23 / LiF buffer layer 24 / A1 layer 25; wherein: the light-emitting layer is made of P1 in the first embodiment.
  • the preparation process of the organic electroluminescent device is:
  • a layer of indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ is deposited on one surface of the glass substrate 21.
  • (ITO) layer 22 forming a conductive layer as an anode, having a thickness of 50-300 nm; preferably ITO having a sheet resistance of 10 ⁇ / ⁇ .
  • Metal aluminum is vacuum-deposited on the light-emitting layer to form a metal aluminum layer 25 as a cathode to obtain the organic electroluminescent device.
  • An organic field effect transistor comprising P1 in the first embodiment
  • An organic field effect transistor having a structure as shown in Fig. 3; the substrate of the present embodiment is doped with a doped silicon wafer (Si) as a substrate.
  • the structure of the organic field effect transistor is: Si 31/440 nm thick SiO 2 insulating layer 32 / octadecyltrichlorosilane (OTS) layer 33 for modifying SiO 2 / organic semiconductor layer 34 / gold-based
  • a SiO 2 insulating layer 32 is coated on one surface of the cleaned doped silicon wafer 31; secondly, a modified octadecyltrichlorosilane is coated on the SiO 2 insulating layer.
  • a layer 33 having a thickness of 10 to 200 nm; then, a layer of an organic semiconductor layer 34 made of P1 in the first embodiment, having a thickness of about 5030-300 nm, is spin-coated on the octadecyltrichlorosilane layer.
  • a source electrode (S) 35 and a drain electrode (D) 36 made of gold but not limited to gold are provided on the organic semiconductor layer at intervals, and the organic field effect transistor is obtained.

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Description

含芴有机半导体材料， 其制备方法和应用 技术领域
本发明涉及一种共聚物有机半导体材料，更具体的涉及一类含芴有机半导体 材料。
本发明还涉及一类含芴有机半导体材料的制备方法及其应用。
背景技术
高效率太阳能电池通常是以无机半导体为原料， 但目前市场上主要的硅晶 太阳能电池由于生产过程工艺复杂， 污染严重， 耗能大， 成本高， 抑制了其商 业化应用的发展。 因此利用廉价材料制备低成本、 高效能的太阳能电池一直是 光伏领域的研究热点和难点。 而有机半导体材料一方面由于有机材料的环境稳 定性好、 制备成本低、 功能易于调制、 柔韧性及成膜性都较好； 另一方面由于 有机太阳能电池加工过程相对简单， 可低温操作， 器件制作成本也较低等优点 而备受关注， 成为廉价和有吸引力的太阳能电池材料。 除此之外， 有机太阳能 电池的潜在优势还包括： 可实现大面积制造、 可使用柔性衬底、 环境友好、 轻 便易携等。
虽然有机太阳能电池得到了较快的发展， 但是仍比无机太阳能电池的转换 效率低得多， 限制其性能提高的主要制约因素有： 有机半导体器件相对较低的 载流子迁移率， 器件的光谱响应与太阳辐射光谱不匹配， 高光子通量的红光区 没有被有效利用以及载流子的电极收集效率低等。 为了使有机太阳能电池得到 实际的应用， 开发新型的材料， 大幅度提高其能量转换效率仍是这一研究领域 的首要任务。
芴由于具有平面分子特性， 结构较为刚性， 因此化学性质稳定； 并且可通 过化学反应在 9位上引入其它支链， 2、 7位上易进行过渡金属交叉偶联， 因此具 有很好的化学可修饰性； 另外它还具有相对较宽的带隙和较低的 HOMO能级， 优良的量子效率、 空穴传输性能和成膜性， 因此芴及其衍生物被广泛应用于光 电材料的研究。 蒽及其衍生物具有很好的稳定性和较好的成膜性； 其紫外可见光谱呈现出 较宽的手指峰吸收， 有利于提高对太阳光的吸收覆盖范围； 并且它具有适当的 载流子传输特性， 其晶体室温下空穴迁移率可达 3 cm2/V-s, 是一类优异的有机 为有机光伏材料的研究却鲜有报道， 这就大大限制了它的应用范围。
而噻吩并 [3,4-c]吡咯 -4,6-二酮的结构简单， 分子中原子位置相对紧凑， 且结 构具有对称性， 当作为含芴有机半导体材料共轭聚合物单元时， 也有很强的吸 电子作用。 通过在吡咯环上增加烷烃链， 也能很好地增加含芴有机半导体材料 共轭聚合物的溶解性和加工性。 目前， 它在有机光电研究领域具有广泛的应用 前景。
发明内容
本发明的目的在于提供一类含芴有机半导体材料， 用于解决上述问题。 本发明的目的还在于提供一类含芴有机半导体材料的制备方法，以及该有机 半导体材料在聚合物太阳能电池， 有机电致发光器件， 有机场效应晶体管， 有 机光存储， 有机非线性器件和有机激光器件等领域中的应用。
本发明所述的一类含芴 机半导体材料具有以下通式（P ):
Figure imgf000004_0001
式中， n为 1~100之间的整数； m为 1~20的整数； 优选 m的取值范围为： 6-12的整数；
x、 y为正实数值， 且 x+y=l ; 且 x+y=l ; x、 y的数值由三种单元体的投料 比决定；
、 R2出现时可相同或不同， 彼此独立地表示单取代或多取代的官能团， 选自氢原子、 氟原子、 氰基、 d - Cu)的直链或带支链的烷基或烷氧基、 芳基、 或杂芳基； 优选 、 R2分别为具有 d ~ C18的直链或带支链的烷基或烷氧基； R3为氢原子、 （^~ 2()的烷基； 优选， R3为 d~C12的烷基。
本发明所设计的一类含芴有机半导体材料， 其制备方案如下：
步骤一： 在无水无氧反应条件下， 将 2, 7-二溴 -9, 9-二烷基芴和正丁基锂 (n-BuLi, 下同 )或叔丁基里 （t-BuLi)在 -70°C ~-85°C下以摩尔比 1: 2 ~ 4力口 入至第二溶剂中， 然后加入 2-异丙氧基 -4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷或 双频哪醇合二硼， 进行缩合反应 12 ~ 48小时， 得到产物， 即 2, 7-双（ 4, 4, 5, 5- 四曱基 -1,3, 2-二杂氧戊硼烷基） -9, 9-二烷基芴； 其中， 第二溶剂为四氢呋喃、 乙醚、 二氯曱烷、 三氯曱烷或乙酸乙酯中的至少一种； 2-异丙氧基 -4, 4, 5, 5-四 曱基 -1, 3, 2-二杂氧戊硼烷或双频哪醇合二硼的摩尔用量为 2, 7-二溴 -9, 9-二烷基 芴的 2~4倍； 缩合反应式如下：
Figure imgf000005_0001
步骤二：在无氧环境中，将结构式为
Figure imgf000005_0002
的 2,7-二 (4,4
四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二烷基芴、 结构式为
Figure imgf000005_0003
溴蒽或其衍生物、结构式为
Figure imgf000005_0004
1,3-二（ 5-溴噻吩基）-噻吩并 [3,4-c] 吡咯 -4,6-二酮或其衍生物按摩尔比 i: j: k混合， JL i=j+k, i, j, k为正实数， 在 70 100 °C、 催化剂、 碱液和第一溶剂存在下， 进行 Suzuki反应 24 ~ 72小时，
Figure imgf000006_0001
的所述含芴有机半 导体材料；其中，催化剂为 Pd(PPh3)4、 Pd(OAc)2、三环己基膦、 Pd2(dba)3/P(o-Tol)3 或 Pd(PPh3)2Cl2; 碱液为 NaOH水溶液、 Na2C03水溶液、 NaHC03水溶液或四乙 基氢氧化铵水溶液， 第一溶剂为曱苯、 乙二醇二曱醚、 四氢呋喃、 乙醚、 二氯 曱烷、三氯曱烷或乙酸乙酯等，催化剂的用量为 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂 氧戊硼烷)基 -9,9-二烷基芴摩尔量的 0.01%~20%,碱的用量为 2,7-二 (4,4,5,5-四曱 基 -1,3,2-二杂氧戊硼烷)基 -9,9-二烷基芴摩尔量的 2~20倍； Suzuki反应式如下：
Figure imgf000006_0002
1. 本发明的有机半导体材料分子中引入了蒽以及 1,3-二（5-溴噻吩基） -噻 吩并 [3,4-c]吡咯 -4,6-二酮基团， 明显改善了其载流子迁移性能和光吸收范围；
2. 本发明的有机半导体材料分子中含有蒽单元， 由于其良好的平面度和共 轭度， 从而提高了其载流子迁移率， 同时， 1,3-二（5-溴噻吩基） -噻吩并 [3,4-c] 吡咯 -4,6-二酮上的 5位引入了烷基等修饰， 提高了其溶解性， 从而提高了其加工 性能；
3. 1,3-二（5-溴噻吩基） -噻吩并 [3,4-c]吡咯 -4,6-二酮的结构简单， 分子中原 子位置相对紧凑， 且结构具有对称性， 当作为含芴有机半导体材料共轭聚合物 单元时， 具有很强的吸电子作用。 釆用 1,3-二（5-溴噻吩基） -噻吩并 [3,4-c]吡咯 -4,6-二酮单元以及蒽单元与芴单元共聚，有效调节该有机半导体材料的带隙，并 将其吸收带边推向红外及近红外区， 使其吸光度强， 对光吸收范围宽， 提高了 其对太阳光的利用率， 同时， 使得该有机半导体材料溶解性能和电荷传输性能 优异；
4. 该有机半导体材料制备方法工艺简单， 产率高， 反应条件温和， 易于操 作和控制， 适合于工业化生产。
附图说明 结构示意图； 构示意图； 管的结构示意图。
具体实施方式
本发明提供的一类含芴有机半导体材料， 具有以下通式（P ):
Figure imgf000007_0001
式中， n为 1~100之间的整数； m为 1~20的整数； 优选 m的取值范围为： 6-12的整数
x、 y为正实数值， 且 x+y=l ; 且 x+y=l ; x、 y的数值由 2,7-二 (4,4,5,5-四曱 基 -1,3,2-二杂氧戊硼烷)基 -9,9-二烷基芴， 9,10-二溴蒽， 1,3-二 （5-溴噻吩基） - 噻吩并 [3 ,4-c]吡咯 -4,6-二酮三种单元体的投料比决定；
、 R2出现时可相同或不同， 彼此独立地表示单取代或多取代的官能团， 选自氢原子、 氟原子、 氰基、 d - Cu)的直链或带支链的烷基或烷氧基、 芳基、 或杂芳基； 优选 、 R2分别为具有 d ~ C18的直链或带支链的烷基或烷氧基；
R3为氢原子、 （^ ~ 2()的烷基； 优选， R3为 d ~ C12的烷基。
一类含芴有机半导体材料， 其制备方案如下：
步骤 S1 : 在无水无氧反应条件下， 将 2, 7-二溴 -9, 9-二烷基芴和正丁基锂在 -70°C ~ -85°C下以摩尔比 1 : 2 ~ 4加入至第二溶剂中， 然后加入 2-异丙氧基 -4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷或双频哪醇合二硼 ( 其摩尔用量为 2, 7-二溴 -9, 9-二烷基芴的 2 ~ 4倍）， 反应 12 ~ 48小时， 得到产物， 即 2, 7-双（4, 4, 5, 5-四 曱基 -1, 3, 2-二杂氧戊硼烷基） - 9, 9-二烷基芴； 其中， 第二溶剂为四氢呋喃、 乙 醚、 二氯曱烷、 三氯曱烷或乙酸乙酯中的至少一种， 其反应式如下：
Figure imgf000008_0001
步骤 S2:在无氧环境中，将 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9- 二烷基芴、 9,10-二溴蒽或其衍生物、 1,3-二（5-溴噻吩基） -噻吩并 [3,4-c]吡咯 -4,6- 二酮或其衍生物按摩尔比 i: j: k混合，且满足 i=j+k, i,j , k为正实数，在 70〜： 100 °C、 催化剂、碱液和第一溶剂下进行 Suzuki反应 24 ~ 72小时， 得到含芴有机半导体 材料聚合物；其中，催化剂为 Pd(PPh3)4、Pd(OAc)2、三环己基膦、 Pd2(dba)3/P(o-Tol)3 或 Pd(PPh3)2Cl2; 碱液为 NaOH水溶液、 Na2C03水溶液、 NaHC03水溶液或四乙 基氢氧化铵水溶液， 第一溶剂为曱苯、 乙二醇二曱醚、 四氢呋喃、 乙醚、 二氯 曱烷、三氯曱烷或乙酸乙酯等，催化剂的用量为 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂 氧戊硼烷)基 -9,9-二烷基芴摩尔量的 0.01%~20%,碱的用量为 2,7-二 (4,4,5,5-四曱 基 -1,3,2-二杂氧戊硼烷)基 -9,9-二烷基芴摩尔量的 2~20倍； 其反应式如下：
Figure imgf000009_0001
本发明的无氧环境是由氮气（N2 )和 /或惰性气体混合构成。
本发明开发了一种含芴的有机半导体材料， 并将其应用于有机太阳能电池 等领域。 该材料具有较低的能隙， 较高的迁移率， 光谱的吸收范围宽， 并且这 种材料有利于载流子在活性层材料内部更为有效地传递。 将本发明中的材料作 为活性材料制备的有机太阳能电池， 经过高温退火后， 能有效增加分子内各基 团和分子链段间排列的有序性和规整度， 提高载流子迁移率的传输速度和效率， 进而提高光电转换效率。
下面结合附图， 对本发明的较佳实施例作进一步详细说明。
实施例 1
本实施例公开结构如下的含芴有机半导体材料聚合物 Pl、 P2:
Figure imgf000009_0002
Pl、 P2的制备步骤如下：
步骤一、 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二辛基芴的制备:
Figure imgf000009_0003
搭好无水无氧反应装置， 在不断搅拌和 N2的保护下， 往三口瓶中加入白色 的 2,7-二溴 -9,9-二辛基芴 9.0mmol, 用注射器注入 150ml精制的四氢呋喃溶剂， 在 -78°C条件下再用注射器慢慢注入 27.0mmol n-BuLi,搅拌反应 2小时。反应 2 小时后，在 -78。C条件下用注射器注入 30.6mmol 2-异丙氧基 -4,4,5,5-四曱基 -1,3,2- 二杂氧戊硼烷， 升温到室温反应过夜。
反应结束后， 加入饱和 NaCl水溶液， 氯仿萃取， 无水硫酸钠干燥， 抽虑后 将滤液收集并旋蒸掉溶剂。 最后将粗产物用石油醚： 乙酸乙酯 (v/v=15:l)为淋洗 液进行硅胶柱层析分离，得到粉末状固体 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼 烷)基 -9,9-二辛基芴， 产率 65%。 GC-MS (EI-m/z): 642 (^)。
步骤二、 Pl、 P2的制备：
Figure imgf000010_0001
PI x=0. 1， y=0. 9
P2 x=0. 5, y=0. 5
在反应器中加入 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二辛基芴 lmmol、 9,10-二溴蒽 O.lmmoL 1,3-二 (5-溴噻吩基) -噻吩并 [3,4-c]吡咯 -4,6-二酮 0.9mmol、 Pd2(dba)30.025mmoK P(o-Tol)30.050 mmoK 2mol/L的 Na2C03水溶液 5ml和曱苯溶剂 30ml, 通过反复进行通 N2和抽真空使反应体系处于无氧状态， 在 70。C条件下反应 70h。
反应 70h后， 往产物的反应瓶中加入去离子水和曱苯进行萃取， 取有机相， 用减压蒸馏的方法将含芴有机半导体材料聚合物 /曱苯溶液蒸干至约 5ml左右， 将其滴入到 300ml无水曱醇中不断搅拌， 并有固体沉淀析出， 经过抽滤、 烘干 后得到固体粉末。 再将固体粉末用氯仿溶解， 用中性氧化铝过层析柱， 除去催 化剂 Pd2(dba)3/P(o-Tol)3, 最后将含芴有机半导体材料聚合物 /氯仿溶液旋蒸至剩 5ml左右，将其滴入曱醇溶剂中并搅拌数小时， 最后将含芴有机半导体材料聚合 物 P1收集烘干。 用索氏抽提器将含芴有机半导体材料聚合物抽提， 从而提高含 芴有机半导体材料聚合物分子量的单分散性。
釆用 Waters Breeze凝胶色谱仪， 将提纯后的含芴有机半导体材料聚合物 P1 溶于精制后的四氢呋喃配成 lmg/lmL溶液， 用仪器专用配套滤膜滤掉不溶物后 以 10微升量， lml/min的进样速度进行 GPC测试， 数均分子量 Mn 69000, 含 芴有机半导体材料聚合物单分散性为 1.31 , n为 100。
在反应器中加入 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二辛基芴 lmmol、 9,10-二溴蒽 0.5mmol、 1,3-二 (5-溴噻吩基) -噻吩并 [3,4-c]吡咯 -4,6-二酮 0.5mmol, 其它物体投料量、 反应条件和后处理方法均不变， 则最终得到含芴有 机半导体材料聚合物 P2。 釆用 Waters Breeze凝胶色语仪， 将提纯后的含芴有机 半导体材料聚合物 P2溶于精制后的四氢呋喃配成 lmg/lmL溶液， 用仪器专用 配套滤膜滤掉不溶物后以 10微升量， lml/min的进样速度进行 GPC测试， 数均 分子量 Mn 41200 , 含芴有机半导体材料聚合物单分散性为 1.46, n为 65。
实施例 2
本实施例 、 P4:
Figure imgf000011_0001
χ=0. 8 , y=0. 2
x=0. 2 , y=0. 8
P3、 P4的制备步骤如下：
步骤一、 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二已基芴的制备： 其制备过程参考实施例 1 中的步骤一， 只是用氩气来构建无氧环境保护气 步骤三、 P3、 P4的制备:
Figure imgf000012_0001
在反应器中加入 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二已基芴 lmmol、 9,10-二溴 -2,6-二 (2-辛基癸基)蒽 0.8mmol (该化合物合成方法参见 Klaus Mullen等人的 Macromol. Chem. Phys. 2006, 207, 1107-1115 )、 1,3-二 (5-溴噻吩 基) -5-曱基-噻吩并 [3 ,4-c]吡咯 -4,6-二酮 0.2mmol、 Pd(OAc)23mg、 2mol/L的 Na2C03 水溶液 10ml和曱苯溶剂 40ml,通过反复进行通氩气和抽真空使反应体系处于无 氧状态， 在 100°C条件下反应 24h。
反应 24h后， 往反应瓶中加入去离子水和曱苯进行萃取， 取有机相， 用减 压蒸馏的方法将含芴有机半导体材料聚合物 /曱苯溶液蒸干至少量， 将其滴入到 300ml无水曱醇中不断搅拌，有固体沉淀析出，经过抽滤、烘干后得到固体粉末。 再将固体粉末用氯仿溶解， 用中性氧化铝过层析柱， 除去催化剂 Pd(OAc)2, 最 后将含芴有机半导体材料聚合物 /氯仿溶液旋蒸至剩 5ml左右， 将其滴入曱醇溶 剂中并搅拌数小时， 最后将含芴有机半导体材料聚合物 P3收集烘干。 用索氏抽 提器将含芴有机半导体材料聚合物抽提， 从而提高含芴有机半导体材料聚合物 分子量的单分散性。
釆用 Waters Breeze凝胶色谱仪， 将提纯后的含芴有机半导体材料聚合物 P3 溶于精制后的四氢呋喃配成 lmg/lmL溶液， 用仪器专用配套滤膜滤掉不溶物后 以 10微升量， lml/min的进样速度进行 GPC测试， 数均分子量 Mn 35800, 含 芴有机半导体材料聚合物单分散性为 1.87 , n为 38。
在反应器中加入 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二己基芴 lmmol、 9,10-二溴 -2,6-二 (2-辛基癸基)蒽 0.2mmol、 1,3-二 (5-溴噻吩基) -5-曱基- 噻吩并 [3,4-c]吡咯 -4,6-二酮 0.8mmol, 其它物体投料量、 反应条件和后处理方法 均不变， 则最终得到含芴有机半导体材料聚合物 P4。 釆用 Waters Breeze凝胶色 语仪， 将提纯后的含芴有机半导体材料聚合物 P4 溶于精制后的四氢呋喃配成 lmg/lmL溶液， 用仪器专用配套滤膜滤掉不溶物后以 10微升量， lml/min的进 样速度进行 GPC测试， 数均分子量 Mn 31500, 含芴有机半导体材料聚合物单 分散性为 2.03 , n为 43。
实施例 3
本实施例公开结构如下的含芴有机半导体材料聚合物 P5、 P6:
Figure imgf000013_0001
P5、 P6的制备步骤如下：
步骤一、 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二 (十二烷基)芴的 制备：
其制备过程参考实施例 1 中的步骤一， 只是用氮气和氩气混合气构建无氧 环境保护气氛。
步骤二、 P5、 P6的制备：
Figure imgf000014_0001
在反应器中加入 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二 (十二烷 基)芴 lmmol、 9,10-二溴 -2-氟蒽 0.5mmol (该化合物的合成方法参见 Elimelech Rochlin等人的 J.Org.Chem., 2003, 68, 216-226 ) 、 1,3-二 (5-溴噻吩基) -5-辛基-噻 吩并 [3,4-c]吡咯 -4,6-二酮 0.5mmol、 Pd(PPh3)40.02mmoK 2mol/L的 Na2C03水溶 液 10ml和曱苯溶剂 40ml,通过反复进行通通氮气和氩气混合气，并抽真空使反 应体系处于无氧状态， 在 80°C条件下反应 58h。
反应 58h后， 往反应瓶中加入去离子水和曱苯进行萃取， 取有机相， 用减 压蒸馏的方法将含芴有机半导体材料聚合物 /曱苯溶液蒸干至少量， 将其滴入到 300ml无水曱醇中不断搅拌，有固体沉淀析出，经过抽滤、烘干后得到固体粉末。 再将固体粉末用氯仿溶解， 用中性氧化铝过层析柱， 除去催化剂 Pd(PPh3)4, 最 后将含芴有机半导体材料聚合物 /氯仿溶液旋蒸至剩 5ml左右， 将其滴入曱醇溶 剂中并搅拌数小时， 最后将含芴有机半导体材料聚合物 P5收集烘干。 用索氏抽 提器将含芴有机半导体材料聚合物抽提， 从而提高含芴有机半导体材料聚合物 分子量的单分散性。
釆用 Waters Breeze凝胶色谱仪， 将提纯后的含芴有机半导体材料聚合物 P5 溶于精制后的四氢呋喃配成 lmg/lmL溶液， 用仪器专用配套滤膜滤掉不溶物后 以 10微升量， lml/min的进样速度进行 GPC测试， 数均分子量 Mn 20300, 含 芴有机半导体材料聚合物单分散性为 2.33 , n 为 25。 在反应器中加入 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二 (十二烷基)芴 lmmol、 9,10-二溴 -2- 氟蒽 0.6mmol、 1,3-二 (5-溴噻吩基) -5-辛基-噻吩并 [3,4-c]吡咯 -4,6-二酮 0.4mmol, 其它物体投料量、 反应条件和后处理方法均不变， 则最终得到含芴有机半导体 材料聚合物 P6。 釆用 Waters Breeze凝胶色语仪， 将提纯后的含芴有机半导体材 料聚合物 P6溶于精制后的四氢呋喃配成 Img/lmL溶液， 用仪器专用配套滤膜 滤掉不溶物后以 10微升量， lml/min的进样速度进行 GPC测试， 数均分子量 Mn~21300, 含芴有机半导体材料聚合物单分散性为 2.16 , n为 27。
实施例 4
本实施例公开结构如下的含芴有机半导体材料聚合物 P7、 P8:
Figure imgf000015_0001
P7、 P8的制备步骤如下：
步骤一、 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二癸基芴的制备: 其制备过程参考实施例 1中的步骤一。
步骤二、 P7、 P8的制备：
Figure imgf000016_0001
在反应器中加入 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二癸基芴 lmmol、 9,10-二溴 -1,4-二曱氧基蒽 0.5mmol (该化合物的合成方法参见 Osman Cakmak等人的 J.Org.Chem., 2006, 71, 1795-1801 ) 、 1,3-二 (5-溴噻吩基) -5-(2-乙 基己基) -噻吩并 [3, 4-c]吡咯 -4,6-二酮 0.5mmol、三环己基膦 5mg、 2mol/L的 Na2C03 水溶液 10ml和曱苯溶剂 50ml, 通过反复进行通 N2和抽真空使反应体系处于无 氧状态， 在 90°C条件下反应 64h。
反应 64h后， 往反应瓶中加入去离子水和曱苯进行萃取， 取有机相， 用减 压蒸馏的方法将含芴有机半导体材料聚合物 /曱苯溶液蒸干至少量， 将其滴入到 300ml无水曱醇中不断搅拌，有固体沉淀析出，经过抽滤、烘干后得到固体粉末。 再将固体粉末用氯仿溶解， 用中性氧化铝过层析柱， 除去催化剂三环己基膦， 最后将含芴有机半导体材料聚合物 /氯仿溶液旋蒸至剩 5ml左右， 将其滴入曱醇 溶剂中并搅拌数小时， 最后将含芴有机半导体材料聚合物 P7收集烘干。 用索氏 抽提器将含芴有机半导体材料聚合物抽提， 从而提高含芴有机半导体材料聚合 物分子量的单分散性。
釆用 Waters Breeze凝胶色谱仪， 将提纯后的含芴有机半导体材料聚合物 P7 溶于精制后的四氢呋喃配成 lmg/lmL溶液， 用仪器专用配套滤膜滤掉不溶物后 以 10微升量， lml/min的进样速度进行 GPC测试， 数均分子量 Mn 56700, 含 芴有机半导体材料聚合物单分散性为 1.43 , n为 73。
在反应器中加入 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二癸基芴 lmmol、 9,10-二溴 -1,4-二曱氧基蒽 0.4mmol、 1,3-二 (5-溴噻吩基) -5-(2-乙基己基) - 噻吩并 [3,4-c]吡咯 -4,6-二酮 0.6mmol, 其它物体投料量、 反应条件和后处理方法 均不变， 则最终得到含芴有机半导体材料聚合物 P8。 釆用 Waters Breeze凝胶色 语仪， 将提纯后的含芴有机半导体材料聚合物 P8 溶于精制后的四氢呋喃配成 lmg/lmL溶液， 用仪器专用配套滤膜滤掉不溶物后以 10微升量， lml/min的进 样速度进行 GPC测试， 数均分子量 Mn 47700, 含芴有机半导体材料聚合物单 分散性为 1.31 , n为 60。
实施例 5
本实施例公开结构如下的含芴有机半导体材料聚合物 P9、 P10:
Figure imgf000017_0001
P9 x=0. 5， y=0. 5
P10 x=0. 1， y=0. 9
P9、 P10的制备步骤如下：
步骤一、 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二辛基芴的制备: 其制备过程参考实施例 1中的步骤一。
步骤二、 P9、 P10的制备：
Figure imgf000018_0001
P9 ^O. 5, y=0. 5
P10 x-0. 1 , y-0. 9
在反应器中加入 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二辛基芴 lmmol、 9,10-二溴 -2-辛基 -6-十八烷氧基蒽 0.5mmol、 1,3-二 (5-溴噻吩基) -5-十二 烷基-噻吩并 [3,4-c]吡咯 -4,6-二酮 0.5mmol、 Pd(PPh3)2Cl2 0.02mmol、 2mol/L 的 Na2C03水溶液 10ml和曱苯溶剂 50ml,通过反复进行通 N2和抽真空使反应体系 处于无氧状态， 在 75°C条件下反应 40h。
反应 40h后， 往反应瓶中加入去离子水和曱苯进行萃取， 取有机相， 用减 压蒸馏的方法将含芴有机半导体材料聚合物 /曱苯溶液蒸干至少量， 将其滴入到 300ml无水曱醇中不断搅拌，有固体沉淀析出，经过抽滤、烘干后得到固体粉末。 再将固体粉末用氯仿溶解， 用中性氧化铝过层析柱， 除去催化剂 Pd(PPh3)2Cl2, 最后将含芴有机半导体材料聚合物 /氯仿溶液旋蒸至剩 5ml左右， 将其滴入曱醇 溶剂中并搅拌数小时， 最后将含芴有机半导体材料聚合物 P9收集烘干。 用索氏 抽提器将含芴有机半导体材料聚合物抽提， 从而提高含芴有机半导体材料聚合 物分子量的单分散性。
釆用 Waters Breeze凝胶色谱仪， 将提纯后的含芴有机半导体材料聚合物 P9 溶于精制后的四氢呋喃配成 lmg/lmL溶液， 用仪器专用配套滤膜滤掉不溶物后 以 10微升量， lml/min的进样速度进行 GPC测试， 数均分子量 Mn 30000, 含 芴有机半导体材料聚合物单分散性为 1.83 , n为 33。
在反应器中加入 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二癸基芴 lmmol、 9,10-二溴 -2-辛基 -6-十八烷氧基蒽 0.1mmol、 1,3-二 (5-溴噻吩基) -5-(2-乙 基己基) -噻吩并 [3 ,4-c]吡咯 -4,6-二酮 0.9mmol, 其它物体投料量、 反应条件和后 处理方法均不变， 则最终得到含芴有机半导体材料聚合物 P10。 釆用 Waters Breeze凝胶色语仪， 将提纯后的含芴有机半导体材料聚合物 P10溶于精制后的 四氢呋喃配成 lmg/lmL溶液， 用仪器专用配套滤膜滤掉不溶物后以 10微升量， lml/min的进样速度进行 GPC测试，数均分子量 Mn 26400,含芴有机半导体材 料聚合物单分散性为 2.01 , n为 30。
本发明还提供了结构式为
Figure imgf000019_0001
(式中， n为 1~100之间的整数； m为 1~20的整数； x、 y为正实数值，且 x+y=l ; 、 R2分别为氢原子、 氟原子、氰基、 d - Cw的直链或带支链的烷基或烷氧基、 芳基、 或杂芳基； R3为氢原子、 d - C^的烷基）的一类含芴有机半导体材料在 聚合物太阳能电池， 有机电致发光， 有机场效应晶体管， 有机光存储， 有机非 线性器件和有机激光器件等领域中的应用。
以下实施例是一类含芴有机半导体材料在有机太阳能电池，有机场效应晶体 管， 有机电致发光器件中的应用。
实施例 6
以实施例一中的 P1作为活性层材料的有机太阳能电池器件
一种有机太阳能电池器件， 其结构如图 1所示。 其中， 本实施例中的衬底釆 用 ITO玻璃， 玻璃作为衬底基材， ITO作为导电层。
该有机太阳能电池器件的结构为： 玻璃 11/ITO层 12/PEDOT:PSS 层 13/活 性层 14/A1层 15; 其中， 活性层的材质为混合物， 包括电子给体材料， PCBM 为电子受体材料；电子给体材料以实施例一中的 P1为材质，电子受体材料为 [6,6] 苯基 -C61 -丁酸曱酯 （简称 PCBM ); ITO是方块电阻为 10-20 Ω/口的氧化铟锡， PEDOT 为聚（3,4-亚乙二氧基噻吩）， PSS 为聚（苯乙烯磺酸）； 优选方块电阻 为 18 Ω/口的 ITO。
该有机太阳能电池器件的制备过程为：
在玻璃基片 11 的一个表面沉积一层方块电阻为 10-20 Ω/口的氧化铟锡 ( ΙΤΟ )层 12, 形成作为阳极的导电层， 厚度约为 50-300 nm;
ITO玻璃经过超声波清洗， 并用氧 -Plasma处理后， 在 ITO表面涂上一层起 修饰作用的 PEDOT:PSS层 13 , 厚度为 20-300 nm;
在聚（3,4-亚乙二氧基噻吩）： PSS 为聚（苯乙烯磺酸）层上釆用旋涂技术 涂覆一层活性层 14, 厚度为 50-300 nm, 该活性层的材质以实施例一中的 P1和 [6,6]苯基 -C61 -丁酸曱酯（简称 PCBM ) 的混合物；
在活性层的表面真空蒸镀金属铝， 形成作为阴极的金属铝层 15, 得到有机 太阳能电池器件；
将有机太阳能电池器件用环氧树脂封装后， 置于 110°C密闭条件下退火 1.5 小时， 再降到室温。 由于器件经过退火后， 材料的化学结构更加规整有序， 提 高了载流子的传输速度和效率， 从而提高了器件的光电转换效率。
优选 ITO、 PEDOT:PSS层、 活性层、 A1层的厚度分别为 150 nm、 50 nm, 120 nm、 100 nm。
实施例 7
以实施例一中的 P1作为有机电致发光器件
一种有机电致发光器件， 其结构如图 2所示； 本实施例中的衬底釆用 ITO 玻璃， 玻璃作为衬底基材， ITO作为导电层。
该有机电致发光器件的结构为： 玻璃 21 /ITO层 22/发光层 23/LiF緩冲层 24/A1层 25; 其中： 发光层以实施例一中的 P1为材质。
该有机电致发光器件的制备过程为：
在玻璃基片 21 的一个表面沉积一层方块电阻为 10-20 Ω/口的氧化铟锡 ( ITO )层 22, 形成作为阳极的导电层， 厚度为 50-300 nm; 优选方块电阻为 10 Ω/口的 ITO。
通过旋涂技术在 ΙΤΟ表面制备一层以实施例一中的 P1为材质的发光层 23 , 厚度约为 50-300 nm;
在发光层上真空蒸镀 LiF, 作为緩冲层 14, 厚度约为 0.3-2 nm;
在所述发光层上真空蒸镀金属铝， 形成作为阴极的金属铝层 25, 得到所述 有机电致发光器件。
实施例 8
以含实施例一中的 P1为材质的有机场效应晶体管
一种有机场效应晶体管， 其结构如图 3 所示； 本实施例中的衬底釆用掺杂 硅片 （Si )作为衬底。
该有机场效应晶体管的结构为： Si 31/440nm厚的 Si02绝缘层 32/用于修饰 Si02的十八烷基三氯硅烷（OTS )层 33/有机半导体层 34 /以金为材质的源电极 ( S ) 35和漏电极（D ) 36; 其中， 有机半导体层以实施例一中的 P1为材质； 其中， 源电极（S )和漏电极（D )材质也可以选用铜材。
该有机场效应晶体管的制备过程为：
首先， 在清洗过后的掺杂硅片 31的一个表面上涂覆一层 Si02绝缘层 32; 其次， 在所述 Si02绝缘层上涂覆一层起修饰作用的十八烷基三氯硅烷层 33 , 厚 度为 10-200 nm; 接着， 在所述十八烷基三氯硅烷层上旋涂一层以实施例一中的 P1为材质的有机半导体层 34, 厚度约为 5030-300 nm; 最后， 在所述有机半导 体层上间隔设置有以金但不仅限于金为材质的源电极（ S ) 35和漏电极（D ) 36, 得到所述有机场效应晶体管。
应当理解的是， 上述针对本发明较佳实施例的表述较为详细， 并不能因此 而认为是对本发明专利保护范围的限制， 本发明的专利保护范围应以所附权利 要求为准。

Claims

权利要求书
1、 下述通式（P ) 的一类含芴有机半导体材料:
Figure imgf000022_0001
式中， n为 1~100之间的整数； m为 1~20的整数；
x、 y为正实数值， 且 x+y=l ;
、 R2分别为氢原子、 氟原子、 氰基、 d - Cw的直链或带支链的烷基或烷 氧基、 芳基、 或杂芳基； R3为氢原子、 d - C^的烷基。
2、 根据权利要求 1所述的一类含芴有机半导体材料， 其特征在于， 所述 m的取值范围为： 6~12的整数； 所述 R 、 R2分别为具有 d ~ C18的直链或带支 链的烷基或烷氧基； 所述 R3为 ~ C12的烷基。
3、 一类含芴有机半导体材料的制备方法， 其特征在于， 包括如下步骤：
在无氧环境中， 将结构式为
Figure imgf000022_0002
的 2,7-二 (4,4,5,5-四曱基
-1,3,2-二杂氧戊硼烷)基 -9,9-二烷基芴、 结构式为
Figure imgf000022_0003
的 9,10-二溴蒽或
R3 其衍生物和结构式为 ^s^s八 「的 1,3-二（5-溴噻吩基） -噻吩并 [3,4-c]吡 咯 -4,6-二酮或其衍生物， 按摩尔比 i: j : k混合， 且满足 i=j+k, 且 i, j , k为正 实数， 于 70 100 °C、 催化剂、 碱液和第一溶剂条件下， 进行 Suzuki反应 24 ~ 72小时，得
Figure imgf000023_0001
的所述含芴 有机半导体材料； 其中，
n为 1 ~ 200的整数， m为 1~20的整数；
x、 y为正实数， 且 x+y=l;
、 R2分别为氢原子、 氟原子、 氰基、 d-C 的烷基、 烷氧基、 芳基、 或 杂芳基； R3为氢原子、 d~C2。的烷基。
4、 根据权利要求 3所述的制备方法，其特征在于，所述 m的取值范围为： 6-12的整数； 所述 、 R2分别为具有 d ~C18的直链或带支链的烷基或烷氧基； 所述 R3为 d~C12的烷基。
5、 根据权利要求 3 所述的制备方法， 其特征在于， 还包括所述 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二烷基芴的制备过程，制备步骤如下：
在无水无氧条件中，将结构式为
Figure imgf000023_0002
的 2, 7-二溴 -9, 9-二烷基芴 和正丁基锂在 -70°C ~-85°C下， 以摩尔比 1: 2~4加入至第二溶剂中， 然后加入 结构式为 的双频哪醇合二硼或者结构式为 、的 2-异丙氧 基 -4, 4, 5, 5-四曱基 -1,3, 2-二杂氧戊硼烷，进行缩合反应 12-48小时，得到结构
Figure imgf000023_0003
的所述 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷) 基 -9,9-二烷基芴。
6、 根据权利要求 5所述的制备方法， 其特征在于， 所述第二溶剂为四氢 呋喃、 乙醚、二氯曱烷、三氯曱烷或乙酸乙酯中的至少一种； 所述 2-异丙氧基 -4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷或双频哪醇合二硼的摩尔量为 2, 7-二溴 -9, 9- 二烷基芴的 2 ~ 4倍。
7、 根据权利要求 3所述的制备方法， 其特征在于， 所述催化剂的摩尔用 量为 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二烷基芴的 0.01%~20%； 所述催化剂为有机钯或有机钯与有机磷配体的混合物；
所述有机钯为 Pd(PPh3)4、 Pd(OAc)2、 Pd2(dba)3或 Pd(PPh3)2Cl2;
所述有机碑配体为三环己基膦或 P(o-Tol)3。
8、 根据权利要求 7所述的制备方法， 其特征在于， 所述有机钯与有机碑 配体的混合物中， 所述有机钯与有机碑配体的摩尔比为 1： 1 ~20。
9、 根据权利要求 3所述的制备方法， 其特征在于， 所述碱液为 NaOH水 溶液、 Na2C03水溶液、 NaHC03水溶液或四乙基氢氧化铵水溶液； 所述碱液的 用量为 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二烷基芴摩尔量的 2~20 倍； 所述第一有机溶剂为曱苯、 乙二醇二曱醚、 四氢呋喃、 乙醚、 二氯曱烷、 三氯曱烷或乙酸乙酯中的至少一种。
10、 一种如权利要求 1 所述的一类含芴有机半导体材料在有机太阳能电 池， 有机电致发光器件， 有机场效应晶体管， 有机光存储， 有机非线性器件和 有机激光器件等领域中的应用。
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