WO2012083515A1 - 一种有机半导体材料及其制备方法和应用 - Google Patents

一种有机半导体材料及其制备方法和应用 Download PDF

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WO2012083515A1
WO2012083515A1 PCT/CN2010/080012 CN2010080012W WO2012083515A1 WO 2012083515 A1 WO2012083515 A1 WO 2012083515A1 CN 2010080012 W CN2010080012 W CN 2010080012W WO 2012083515 A1 WO2012083515 A1 WO 2012083515A1
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organic
semiconductor material
organic semiconductor
tetradecyl
material according
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PCT/CN2010/080012
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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 EP10860953.8A priority Critical patent/EP2657226B1/en
Priority to PCT/CN2010/080012 priority patent/WO2012083515A1/zh
Priority to US13/884,910 priority patent/US20130225782A1/en
Priority to CN201080069679.XA priority patent/CN103153953B/zh
Priority to JP2013543495A priority patent/JP5667704B2/ja
Publication of WO2012083515A1 publication Critical patent/WO2012083515A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof
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    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
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    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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    • 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
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence
    • C08G2261/522—Luminescence fluorescent
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    • C08G2261/526—Luminescence used as active layer in lasers
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/92—TFT applications
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    • 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
    • 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
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an organic semiconductor material, and more particularly to an organic semiconductor material containing a carbazole unit.
  • the invention also relates to a method of preparing an organic semiconductor material and its use. Background technique
  • 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 portability.
  • 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 top priorities 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 also has a relatively wide band gap and a low HOMO level, excellent quantum efficiency, hole transport properties and film formation, so ⁇ and its derivatives Biology is widely used in the study of photovoltaic materials. Summary of the invention
  • an object of the present invention is to provide an organic semiconductor material containing a carbazole unit.
  • the invention provides a machine semiconductor material having the following general formula (P):
  • R 2 is selected from a hydrogen atom, a fluorine atom, a cyano group, an optionally substituted or unsubstituted linear or branched alkyl or alkoxy group having 1 to 40 C atoms, or an optionally substituted or unsubstituted Aryl or heteroaryl; preferably, R 2 is an optionally substituted or unsubstituted linear or branched alkyl or alkoxy group having 1 to 18 C atoms;
  • R 3 is selected from alkyl of dC ⁇ ; preferably R 3 is C 6 -C 17 alkyl;
  • n is a natural number, and 1 ⁇ n ⁇ 100;
  • n is a natural number, and 1 ⁇ m ⁇ 20, preferably 6 ⁇ m ⁇ 12;
  • the ratio of the feed ratio of the three reactant units such as alkynyl-9,9-dialkylfluorene, 9,10-dibromofluorene or a derivative thereof and carbazole or a derivative thereof is determined.
  • a method for preparing the above organic semiconductor material comprising the steps of:
  • the first solvent is at least one of tetrahydrofuran, diethyl ether, dichlorodecane, trichlorodecane or ethyl acetate; the 2-isopropoxy-4, 4,
  • the molar amount of 5,5-tetradecyl-1,3,2-dioxaborolane is 2 to 4 times the molar amount of the 2,7-dibromo-9,9-dialkylfluorene.
  • the second solvent is at least one of benzene, chlorobenzene, toluene, ethylene glycol dioxime ether, tetrahydrofuran, diethyl ether, dichlorodecane, trichlorodecane or ethyl acetate.
  • the catalyst is organic palladium (eg, Pd(PPh 3 ) 4 , Pd(OAc) 2 , Pd 2 (dba) 3 or Pd(PPh 3 ) 2 Cl 2 ) or organic palladium and organic tablet ligands (three a mixture of cyclohexylphosphine, P(o-Tol) 3 ), a mixture of an organic palladium and an organophosphorus ligand, such as Pd 2 (dba) 3 /P(o-Tol) 3 ; , the amount of 7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan))-9,9-dialkylfluorene is 0.0005 to 0.2 times;
  • the alkali solution is at least one of an aqueous solution of NaOH, an aqueous solution of Na 2 CO 3 , an aqueous solution of NaHCO 3 or an aqueous solution of tetraethylammonium
  • the material of the present invention contains a ruthenium unit, and its carrier mobility is improved due to its good flatness and conjugation degree. At the same time, the N atom in the carbazole is easily introduced with an alkyl group or the like, thereby improving its Solubility, thereby improving its processing properties; 2.
  • the structure of carbazole is simple, the atomic position in the molecule is relatively compact, and the structure has symmetry. When used as a conjugated polymer unit, it has a strong electron donating effect.
  • the carbazole unit and the ruthenium unit are copolymerized with the ruthenium unit to effectively adjust the band gap of the material, so that the absorbance is strong, the light absorption range is wide, the utilization of sunlight is improved, and the dissolution property of the material is improved. Excellent charge transfer performance;
  • the preparation method of the material is simple in process, mild in reaction condition, easy to operate and control, and suitable for industrial production.
  • Figure 1 is a fifth embodiment.
  • Figure 4 is the embodiment 7 to.
  • the invention provides an organic semiconductor material having the following general formula (P):
  • R 2 is selected from a hydrogen atom, a fluorine atom, a cyano group, optionally substituted or unsubstituted, having 1 to 40 a linear or branched alkyl or alkoxy group of a C atom, or an optionally substituted or unsubstituted aryl or heteroaryl group; preferably, R 2 is optionally substituted or unsubstituted having 1 to 18 C a linear or branched alkyl or alkoxy group of an atom;
  • R 3 is selected from alkyl of dC ⁇ ; preferably R 3 is C 6 -C 17 alkyl;
  • n is a natural number, and 1 ⁇ n ⁇ 100;
  • n is a natural number, and 1 ⁇ m ⁇ 20, preferably 6 ⁇ m ⁇ 12;
  • the invention also provides a preparation method of the above organic semiconductor material, comprising the following steps: Step S1, 2,7-dibromo-9,9-dialkylfluorene and n-butyllithium in an anhydrous and oxygen-free environment (n-BuLi) is added to the first solvent at a molar ratio of 1.0: 2.0 to 1.0: 4.0 at -70 ° C to -85 ° C, followed by the addition of 2-isopropoxy-4, 4, 5, 5- Tetradecyl-1,3,2-dioxaborolane (or dipinacol diboron) (2.0 to 4.0 in molar amount of 2,7-dibromo-9,9-dialkylfluorene) Double), the temperature is raised to 20-30 ° C, and the reaction is carried out for 12 to 48 hours to obtain the product, that is, 2, 7-bis( 4, 4, 5, 5-tetradecyl-1,3,2-dioxaboropentyl boron Alkyl) - 9, 9-dialky
  • n is a natural number, and 1 ⁇ m ⁇ 20, preferably 6 ⁇ m ⁇ 12;
  • the catalyst is Organic palladium (eg, Pd(PPh 3 ) 4 , Pd(OAc) 2 , Pd 2 (dba) 3 or Pd(PPh 3 ) 2 Cl 2 ) or organopalladium with an organic ligand (eg, tricyclohexylphosphine, a mixture of P(o-Tol) 3 ), for example, Pd 2 (dba) 3 /P(o-
  • R 2 is selected from a hydrogen atom, a fluorine atom, a cyano group, an optionally substituted or unsubstituted linear or branched alkyl or alkoxy group having 1 to 40 C atoms, or an optionally substituted or unsubstituted Aryl or heteroaryl; preferably, R 2 is an optionally substituted or unsubstituted linear or branched alkyl or alkoxy group having 1 to 18 C atoms;
  • R 3 is selected from alkyl of dC ⁇ ; preferably R 3 is C 6 -C 17 alkyl;
  • n is a natural number, and 1 ⁇ n ⁇ 100;
  • ruthenium 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 appropriate loading.
  • the carrier transport property which has a hole mobility of 3 cm 2 /Vs at room temperature, is an excellent class of organic semiconductor materials.
  • the present invention develops an organic semiconductor material containing a carbazole unit and applies it to fields such as organic solar cells.
  • the material has a lower energy gap, a higher mobility, a wider spectral absorption range, and this material facilitates the more efficient transport of carriers within the active layer material. It can effectively increase the order and regularity of the arrangement between the groups and molecular segments in the molecule, improve the transport speed and efficiency of carrier mobility, and further improve the photoelectric conversion efficiency.
  • the technical examples of the present invention are further illustrated by specific examples and illustrations, including material preparation and organic materials in organic solar cells, organic field effect transistors, organic electroluminescent devices. Applications in the fields of organic optical storage, organic nonlinear materials or organic laser devices, but these examples do not limit the invention.
  • the oxygen-free atmosphere formed in the oxygen-free environment is mainly a nitrogen atmosphere, and may be another inert gas atmosphere; it is not limited thereto.
  • the purified 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 to a volume of 10 ⁇ l, lml.
  • the injection speed of /min was tested by GPC, the number average molecular weight was Mn ⁇ 63000, and the monodispersity of the organic semiconductor material was 1.46, and n was 100.
  • the purified organic semiconductor material polymer P2 is dissolved in purified tetrahydrofuran into a 1 mg/lmL solution using a Waters Breeze gel color smear, and the insoluble matter is filtered off with an instrument-specific filter membrane to a volume of 10 microliters.
  • the injection speed of lml/min was subjected to GPC test, and the number average molecular weight was Mn 39000.
  • the monodispersity of the organic semiconductor material polymer was 1.79 and n was 65.
  • Example 2 This example discloses organic semiconductor material polymers P3, P4 having the following structure:
  • step S1 the temperature is -75 ° C, the temperature is raised to 23 ° C, and the reaction time is 48 hours; 2, 7-dibromo-9,9-dihexyl fluorene and n-butyl lithium are in a molar ratio of 1:2; the solvent is diethyl ether.
  • the molar amount of 2-isopropoxy-4,4,5,5-tetradecyl-1,3,2-dioxaborolane is 2,7-dibromo-9,9-dihexylfluorene Molar amount
  • the organic semiconductor material polymer/anthraquinone solution was evaporated to dryness by at least an amount, and it was dropped into 300 ml.
  • the water is continuously stirred, and a solid precipitates out, and after suction filtration and drying, a solid powder is obtained.
  • the solid powder was dissolved in chloroform, the column was removed by neutral alumina, and the catalyst was removed.
  • the organic semiconductor material polymer/chloroform solution was rotary-screwed to about 5 ml, and it was dropped into a methanol solvent and stirred for several hours.
  • the organic semiconductor material polymer P3 is collected and dried.
  • the organic semiconductor material polymer is extracted by a Soxhlet extractor to increase the monodispersity of the molecular weight of the organic semiconductor material polymer.
  • the purified organic semiconductor material polymer P3 is dissolved in purified tetrahydrofuran to form an Img/lmL solution, which is insoluble by the instrument-specific filter membrane.
  • the GPC test was carried out at a sampling rate of 10 ⁇ l and a throughput of 1 ml/min.
  • the number average molecular weight was Mn ⁇ 34500, and the monodispersity of the organic semiconductor material was 2.24, and n was 37.
  • Embodiment 3 This embodiment discloses organic semiconductor material 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 :
  • step S1 the temperature is -85 ° C, the temperature is raised to 30 ° C, and the reaction time is 22 hours; 2, 7-dibromo-9,9-di(dodecyl)phosphonium and n-butyllithium are in a molar ratio of 1: 2.8;
  • the solvent is trichlorodecane; 2-isopropoxy-4,4,5,5-tetradecyl-1,3,2-dioxaoxyborane is used in a molar amount of 2,7-dibromo 2-fold of the molar amount of -9,9-di(dodecyl)phosphonium.
  • Step 2 Preparation of Step 2, P5 and P6:
  • the organic semiconductor material polymer/anthraquinone solution was evaporated to dryness by at least an amount, and it was dropped into 300 ml.
  • the water is continuously stirred, and a solid precipitates out, and after suction filtration and drying, a solid powder is obtained.
  • the solid powder was dissolved in chloroform, the column was removed by neutral alumina, and the catalyst was removed.
  • the organic semiconductor material polymer/chloroform solution was rotary-screwed to about 5 ml, and it was dropped into a methanol solvent and stirred for several hours.
  • the organic semiconductor material polymer P5 is collected and dried.
  • the organic semiconductor material polymer is extracted by a Soxhlet extractor to increase the monodispersity of the molecular weight of the organic semiconductor material polymer.
  • the purified organic semiconductor material polymer P5 is dissolved in purified tetrahydrofuran to form an Img/lmL solution, and the insoluble matter is filtered off with an instrument-specific filter membrane to 10 ⁇ l, lml /min injection rate for GPC test, number average molecular weight Mn ⁇ 20000, the organic semiconductor material polymer monodispersity is 2.71, and n is 26.
  • the purified organic semiconductor material polymer P6 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 microliters, using a Waters Breeze gel color tone meter.
  • the injection speed of lml/min was subjected to GPC test, and the number average molecular weight was Mn 21000.
  • the monodispersity of the organic semiconductor material polymer was 2.94, and n was 28.
  • Embodiment 4 This embodiment discloses organic semiconductor material polymers P7 and P8 having the following structure:
  • step S1 the temperature is -80 ° C, the temperature is raised to 22 ° C, and the reaction time is 36 hours; 2, 7-dibromo-9,9-dimercaptopurine and n-butyllithium are in a molar ratio of 1:4; Dichloromethane; 2-isopropoxy-4,4,5,5-tetradecyl-1,3,2-dioxaborolane in a molar amount of 2,7-dibromo-9,9 - 4 times the molar amount of diterpene.
  • the organic semiconductor material polymer/anthraquinone solution was evaporated to dryness by at least an amount, and it was dropped into 300 ml.
  • the water is continuously stirred, and a solid precipitates out, and after suction filtration and drying, a solid powder is obtained.
  • the solid powder was dissolved in chloroform, the column was removed by neutral alumina, and the catalyst was removed.
  • the organic semiconductor material polymer/chloroform solution was rotary-screwed to about 5 ml, and it was dropped into a methanol solvent and stirred for several hours.
  • the organic semiconductor material polymer P7 is collected and dried.
  • the organic semiconductor material polymer is extracted by a Soxhlet extractor to increase the monodispersity of the molecular weight of the organic semiconductor material polymer.
  • the purified 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 to a volume of 10 ⁇ l, lml.
  • the injection speed of /min was tested by GPC, the number average molecular weight was Mn ⁇ 55000, and the monodispersity of the organic semiconductor material was 2.31, and n was 72. 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaoxyborane)--9,9-diindenyl ⁇ lmmol, 9, was added to the reactor.
  • the organic semiconductor material polymer P8 is finally obtained.
  • the purified 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 a volume of 10 microliters, using a Waters Breeze gel color tone meter.
  • Example 5 The preparation of an organic solar cell device using the P1 organic semiconductor material of Example 1 as an active layer material is shown in Fig. 1.
  • An organic solar cell device the structure of which is: glass 11 / indium tin oxide (ITO) layer 12 / PEDOT: PSS layer 13 / active layer 14 / A1 layer 15; wherein the material of the active layer 14 contains an electron donor material And electron acceptor material, the electron donor material is the P1 organic semiconductor material in Example 1, [6,6] phenyl-C 61 -butyric acid decanoate (PCBM ) as an electron acceptor material, and ITO is a sheet resistor.
  • ITO indium tin oxide
  • PEDOT PEDOT
  • PSS layer 13 PSS layer 13 / active layer 14 / A1 layer 15
  • the electron donor material is the P1 organic semiconductor material in Example 1, [6,6] phenyl-C 61 -butyric acid decanoate (PCBM ) as an electron acceptor material
  • ITO is a sheet resistor.
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • PSS poly(styrenesulfonic acid)
  • ITO glass is ultrasonically cleaned and treated with oxygen-Plasma Spin-coated PEDOT:PSS jam on ITO.
  • the material is prepared by spin-coating technique.
  • the metal aluminum electrode is prepared by vacuum evaporation to obtain an organic solar cell device.
  • the organic solar cell device is encapsulated with epoxy resin and placed at 110°. C is annealed for 1.5 hours under closed conditions and then lowered to room temperature. Since the organic solar cell device is annealed, the chemical structure of the material is more regular and orderly, which improves the transport speed and efficiency of carriers, thereby improving the organic solar cell device. Photoelectric conversion Change efficiency.
  • the thicknesses of the ITO layer, the PEDOT:PSS layer, the active layer, and the A1 layer are 110 nm, 40 nm, 80 nm, and 120 nm, respectively.
  • Effective side of the prepared battery The product was 9 square millimeters and the measurements were made under a solar simulator. The intensity of the light was verified using a silicon standard cell and the IV curve was measured with a Keithley 2400. The IV curve of the device under simulated illumination conditions of 100 milliwatts per square centimeter is shown in Figure 2. The open circuit voltage is 0.25 volts, the short circuit current is 0.045 mA, the fill factor is 0.35, and the energy conversion efficiency is 0.044%.
  • Embodiment 6 is an organic electroluminescent device using the P1 organic semiconductor material in Embodiment 1 as a light-emitting layer, and its structure is as shown in FIG. 3:
  • An organic electroluminescent device which is structured to: deposit a layer of indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ on a glass substrate 21 as a transparent anode, by spin coating technique on the ITO layer
  • a light-emitting layer 23 made of the P1 organic semiconductor material in the first embodiment is prepared on the second layer, and then LiF is vacuum-deposited on the light-emitting layer 23 as a buffer layer 24, and finally the metal A1 layer 25 is evaporated as a device.
  • Embodiment 7 An organic field effect transistor comprising the P1 organic semiconductor material of Example 1 has a structure as shown in Fig. 4:
  • An organic field effect transistor using a silicon wafer (Si) as the substrate 31, and 450 nm thick SiO 2 is spin-coated on the octadecyltrichlorosilane (OTS) layer 33 for modifying the SiO 2 layer 32, Gold (which may also be made of other metal materials, aluminum, platinum, silver) as the electrode source electrode (S) 35 and the drain electrode (D) 36 are disposed on the organic semiconductor layer 34, thereby producing an airport effect containing P1. Transistor. It is to be understood that the above description of the preferred embodiments of the invention is in no way intended to be construed as limiting the scope of the invention.

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Description

一种有机半导体材料及其制备方法和应用 技术领域
本发明涉及一种有机半导体材料，更具体的涉及为一种含咔唑单元的有 机半导体材料。 本发明还涉及一种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。 发明内容
基于上述问题，本发明的目的在于提供一种含咔唑单元的有机半导体材 料。
本发明提供的一种 机半导体材料， 具有以下通式（P ):
Figure imgf000003_0001
式中：
、 R2选自氢原子、 氟原子、 氰基、 任选取代或未取代的具有 1-40个 C原子的直链或带支链的烷基或烷氧基、 或者任选取代或未取代的芳基或 杂芳基；优选 、 R2为任选取代或未取代的具有 1-18个 C原子的直链或带 支链的烷基或烷氧基；
R3选自 d-C^的烷基； 优选 R3为 C6-C17的烷基；
n为自然数， 且 1 < n≤100;
m为自然数， 且 1 < m<20, 优选 6<m<12;
x、 y为正实数值，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、 9,10-二溴蒽或其衍生物以及咔唑或其衍生 物等三种反应物单元体的投料比决定。
上述有机半导体材料的制备方法， 其包括如下步骤：
Sl、 无水无氧环境下， 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 ~ 1 :4加入至第一溶剂中溶解，然后加入 2-异丙氧基 -4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷或者双频哪醇合二硼， 升温到 20~30°C , 反应 12 - 48小时， 得到 2, 7-双（4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷基 ) - 9, 9-二坑基芴；
S2、 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以及咔唑或其衍生物， 以摩尔比 m:j :k , 且 m=j+k, 加入到含有催化剂和碱溶液的第二溶剂中， 在 70°C ~ 100°C下进 行 Suzuki反应 24 ~ 72小时， 得到所述有机半导体材料。
上述制备方法的 S1步骤中， 所述第一溶剂为四氢呋喃、 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, 2-二杂氧戊硼烷的摩尔用量为所述 2, 7-二溴 -9, 9-二烷基芴摩尔用量的 2 ~ 4倍。
上述制备方法的 S2步骤中， 所述第二溶剂为苯、 氯苯、 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； 所述催化剂为有机钯（如， Pd(PPh3)4、 Pd(OAc)2、 Pd2(dba)3或 Pd(PPh3)2Cl2 ) 或有机钯与有机碑配体（三环己基膦、 P(o-Tol)3 )的混合物， 有机钯与有机 磷配体的混合物， 如 Pd2(dba)3/P(o-Tol)3; 所述催化剂的用量为所述 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二烷基芴摩尔用量的 0.0005~0.2 倍； 所述碱溶液为 NaOH水溶液、 Na2C03水溶液、 NaHC03水溶液或四乙 基氢氧化铵水溶液中的至少一种； 所述碱溶液中碱的摩尔用量为所述 2, 7- 双（4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷基） - 9, 9-二烷基硅芴摩尔用量的 2-20倍。 体管， 有机电致发光器件， 有机光存储， 有机非线性材料和有机激光器件 中。
与现有技术相比， 本发明的主要优点在于：
1. 本发明的材料中含有蒽单元， 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， 咔唑中 N原子上容易引入烷基等修饰， 提高 了其溶解性， 从而提高了其加工性能； 2. 咔唑的结构简单， 分子中原子位置相对紧凑， 且结构具有对称性， 当作为共轭聚合物单元时， 具有较强的给电子作用。 釆用咔唑单元以及蒽 单元与芴单元共聚， 有效调节该材料的带隙， 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， 使得该材料溶解性能和电荷传 输性能优异；
3. 该材料的制备方法工艺简单， 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
图 1是实施例 5以.
池器件的结构示意图
图 2是实施例 5 ,
池器件的 I-V曲线图
图 3是实施例 6
Figure imgf000005_0001
器件的结构示意图；
图 4是实施例 7以.
效应晶体管器件的结构示意图 具体实施方式
本发明提供的一种有机半导体材料， 具有以下通式（P ):
Figure imgf000005_0002
式中：
、 R2选自氢原子、 氟原子、 氰基、 任选取代或未取代的具有 1-40个 C原子的直链或带支链的烷基或烷氧基、 或者任选取代或未取代的芳基或 杂芳基；优选 、 R2为任选取代或未取代的具有 1-18个 C原子的直链或带 支链的烷基或烷氧基；
R3选自 d-C^的烷基； 优选 R3为 C6-C17的烷基；
n为自然数， 且 1 < n≤100;
m为自然数， 且 1 < m<20, 优选 6<m<12;
x、 y为正实数值， 且 x+y=l , x、 y的数值由三种反应物单元体， 即 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 生物以及咔唑或其衍生物的投料比决定。
本发明还提供了一种上述有机半导体材料的制备方法， 包括如下步骤： 步骤 Sl、 在无水无氧环境下， 将 2, 7-二溴 -9, 9-二烷基芴和正丁基锂 ( n-BuLi )在 -70°C ~ -85°C下以摩尔比 1.0: 2.0 ~ 1.0: 4.0加入至第一溶剂 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 2.0 ~ 4.0倍）， 升温到 20-30 °C ,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， 第一溶剂为四氢呋喃、 乙醚、 二 氯曱烷、 三氯曱烷或乙酸乙酯等； 其反应式如下：
Figure imgf000006_0001
式中， m为自然数， 且 1 < m≤20, 优选 6≤m≤12;
步骤 S2、在无氧环境下，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、 咔唑或其衍生物， 以摩尔比 m:j:k, 且 m=j+k, 加入含有催化剂和碱溶液的第二溶剂中， 于 70 100 °C下 进行 Suzuki反应 24 ~ 72小时， 得到有机半导体材料； 其中， 所述催化剂 为有机钯（如， Pd(PPh3)4、 Pd(OAc)2、 Pd2(dba)3或 Pd(PPh3)2Cl2 )或有机钯 与有机碑配体（如，三环己基膦、 P(o-Tol)3 )的混合物，如， Pd2(dba)3/P(o-Tol)3； 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 0.0005 0.2;碱溶液为 NaOH水溶液、 Na2C03水溶液、 NaHC03 水溶液或四乙基氢氧化铵水溶液， 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； 第二溶剂为苯、 氯苯、 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； 其反应式如下：
Figure imgf000007_0001
式中，
、 R2选自氢原子、 氟原子、 氰基、 任选取代或未取代的具有 1-40个 C原子的直链或带支链的烷基或烷氧基、 或者任选取代或未取代的芳基或 杂芳基；优选 、 R2为任选取代或未取代的具有 1-18个 C原子的直链或带 支链的烷基或烷氧基；
R3选自 d-C^的烷基； 优选 R3为 C6-C17的烷基；
n为自然数， 且 1 < n≤100;
x、 y为正实数值， 且 x+y=l , x、 y的数值由三种反应物单元体的投料 比决定。 由于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, 是一类优异的有机半导体材料。 虽然蒽及其衍生物作为有机电致发光材料 的报道已有很多， 但作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。
咔唑的结构简单， 其结构式
Figure imgf000008_0001
分子中原子位置相对紧凑， 且结构具有对称性， 当作为共轭有机半导 体材料聚合物单元时， 也有较强的供电子作用。 目前， 咔唑类化合物已成 为有机光器等研究领域中的热门材料。
本发明开发了一种含咔唑单元的有机半导体材料， 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。 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。 为了更好地理解本发明专利的内容， 下面通过具体的实例和图例来进 一步说明本发明的技术案， 具体包括材料制备和该有机材料在有机太阳能 电池， 有机场效应晶体管， 有机电致发光器件， 有机光存储， 有机非线性 材料或有机激光器件等领域中的应用， 但这些实施实例并不限制本发明。
本实施例中， 无氧环境中所形成的无氧气氛主要为氮气气氛， 也可以 是其它的惰性气体气氛； 在此对其不进行限制。 实施例 物 Pl、 P2:
Figure imgf000009_0001
PI x=0. 1， y=0. 9
P2 x=0. 5， y=0. 5
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_0002
搭好无水无氧反应装置， 在不断搅拌和 Ν2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 2小 时。 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 20°C , 反应 14小时。
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 χ=0. 1， y=0. 9
Ρ2 χ=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 ImmoK 9,10-二溴蒽 O.lmmoK 2,7-二溴 -9-己基 -咔唑 0.9mmol、 四三 苯基膦钯 0.025mmol、 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 72h。
反应 72h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，最后将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， 最后将有机半导体材料聚合物 P1收集烘干。 用索氏抽提器将有机半导体材料聚合物抽提， 从而提高有机 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~63000, 有机半导体材料聚合物单分散性为 1.46, 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 ImmoK 9,10-二溴蒽 0.5mmol、 2,7-二溴 -9-己基 -咔唑 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， 将提纯后的有机半导体材料聚 合物 P2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 39000, 有机半导体材料聚合物单分散性为 1.79 , n为 65。 实施例 2 本实施例公开结构如下的有机半导体材料聚合物 P3、 P4:
Figure imgf000011_0001
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， 不同之处在于：
步骤 S1中， 温度为 -75°C , 升温到 23 °C , 反应时间 48小时； 2, 7-二溴 -9, 9-二己基芴和正丁基锂以摩尔比 1 :2;溶剂为乙醚； 2-异丙氧基 -4, 4, 5, 5- 四曱基 -1, 3, 2-二杂氧戊硼烷的摩尔用量为 2, 7-二溴 -9, 9-二己基芴摩尔量的
3倍。
步骤三、 P3、 P4的制备：
Figure imgf000012_0001
x=0. 8， y=0. 2
x=0. 2， y=0. 8
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 )、2,7- 二淡 _9_(2-乙基己基) -咔唑 0.2mmol、 醋酸钯 3mg、 2mol/L的 Na2C03水溶液 10ml和曱苯溶剂 40ml, 通过反复进行通 N2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， 最后将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， 最后将有机半导体材料聚合物 P3收集烘干。 用索氏抽提器将有机半导体材料聚合物抽提， 从而提高有机半导体材料聚 合物分子量的单分散性。
釆用 Waters Breeze凝胶色谱仪，将提纯后的有机半导体材料聚合物 P3 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~34500, 有机半导体材料聚合物单分散性为 2.24, n为 37。
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、 2,7-二溴 -9-(2-乙基 己基) -咔唑 0.8mmol, 其它物体投料量、 反应条件和后处理方法均不变， 则 最终得到有机半导体材料聚合物 P4。 釆用 Waters Breeze凝胶色谱仪， 将提 纯后的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 30400 , 有机半导体材料聚合物单分散性 为 2.11 , n为 44。 实施例 3 本实施例公开结构如下的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， 不同之处在于：
步骤 S1中， 温度为 -85°C , 升温到 30°C , 反应时间 22小时； 2, 7-二溴 -9, 9-二（十二烷基） 芴和正丁基锂以摩尔比 1 :2.8; 溶剂为三氯曱烷； 2-异 丙氧基 -4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷的摩尔用量为 2, 7-二溴 -9, 9- 二（十二烷基） 芴摩尔量的 2倍。 步 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 ) 、 2,7-二溴 -9-十二 烷基 -咔唑 0.5mmol、四三苯基膦钯 0.02mmol、2mol/L的 Na2C03水溶液 10ml 和曱苯溶剂 40ml, 通过反复进行通 N2和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， 最后将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， 最后将有机半导体材料聚合物 P5收集烘干。 用索氏抽提器将有机半导体材料聚合物抽提， 从而提高有机半导体材料聚 合物分子量的单分散性。
釆用 Waters Breeze凝胶色谱仪，将提纯后的有机半导体材料聚合物 P5 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~20000, 有机半导体材料聚合物单分散性为 2.71 , n为 26。
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、 2,7-二溴 -9-十二烷基 -咔唑 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， 将提纯后的有机 半导体材料聚合物 P6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 21000, 有机半导体材料聚合物单分散性为 2.94 , n为 28。 实施例 4 本实施例公开结构如下的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， 不同之处在于：
步骤 S1中， 温度为 -80°C , 升温到 22°C , 反应时间 36小时； 2, 7-二溴 -9, 9-二癸基芴和正丁基锂以摩尔比 1 :4; 溶剂为二氯曱烷； 2-异丙氧基 -4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷的摩尔用量为 2, 7-二溴 -9, 9-二癸基芴摩尔 量的 4倍。
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 )、 2,7-二庚 -9-(1- 辛基壬基) -咔唑 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， 最后将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， 最后将有机半导体材料聚合物 P7收集烘干。 用索氏抽提器将有机半导体材料聚合物抽提， 从而提高有机半导体材料聚 合物分子量的单分散性。
釆用 Waters Breeze凝胶色谱仪，将提纯后的有机半导体材料聚合物 P7 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~55000, 有机半导体材料聚合物单分散性为 2.31 , n为 72。 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、 2,7-二溴 -9-(1-辛基壬基) - 咔峻 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 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 46800 , 有机半导体材料聚合物单分散性为 2.57 , n 为 60。 实施例 5、 以实施例 1 中的 P1有机半导体材料作为活性层材料的有机 太阳能电池器件的制备， 其结构如图 1所示。
一个有机太阳能电池器件， 其结构设置为： 玻璃 11/氧化铟锡（ITO ) 层 12 /PEDOT:PSS层 13/活性层 14/A1层 15; 其中， 活性层 14的材料包含 有电子给体材料和电子受体材料， 电子给体材料为实施例 1中的 P1有机半 导体材料， [6,6]苯基 -C61 -丁酸曱酯（简称 PCBM )作为电子受体材料， 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)； ITO玻璃经过超声波清洗后， 用氧 -Plasma处理， 在 ITO上旋涂 PEDOT:PSS„ 材料釆用旋涂技术， 金属铝电极通过真空蒸镀技术制备， 得到有机太阳能 电池器件。 将该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。 由于有机太阳能电池器件经过退火后， 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 高了有机太阳能电池器件的光电转换效率。
以实施例 1 中的 P1材料为例， ITO层、 PEDOT:PSS层、 活性层、 A1 层的厚度分别为 110 nm、 40 nm、 80 nm、 120 nm。 制备好的电池的有效面 积为 9平方毫米， 测量是在太阳光模拟器下进行的， 光的强度用硅标准电 池进行校验， I-V曲线用 Keithley 2400进行测量。该器件在 100毫瓦每平方 厘米的模拟光照条件下的 I-V曲线如图 2所示。 开路电压为 0.25伏， 短路 电流为 0.045毫安， 填充因子为 0.35 , 能量转换效率为 0.044%。 实施例 6、 以实施例 1中的 P1有机半导体材料作为发光层的有机电致 发光器件， 其结构如图 3所示：
一种有机电致发光器件， 其结构设置为： 在一个玻璃基片 21上沉积一 层方块电阻为 10-20 Ω/口的氧化铟锡层 22, 作为透明阳极， 通过旋涂技术 在 ITO层 22上制备一层以实施例 1中的 P1有机半导体材料为材质的发光 层 23 , 再在此发光层 23上真空蒸镀 LiF, 作为緩冲层 24 , 最后蒸镀金属 A1层 25 , 作为器件的阴极。 实施例 7、以含有实施例 1中的 P1有机半导体材料的有机场效应晶体 管， 其结构如图 4所示：
一种有机场效应晶体管，釆用硅片（Si )作为衬底 31 , 450 nm厚的 Si02 旋涂到用于修饰 Si02层 32的十八烷基三氯硅烷（OTS )层 33上， 釆用金 (也可以釆用其他金属材质， 铝、 铂、 银）作为电极源电极（S ) 35和漏电 极（D ) 36设置在有机半导体层 34上， 从而制得含有 P1的有机场效应晶 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 P ) 的有机半导体材料:
Figure imgf000019_0001
式中：
、 R2选自氢原子、 氟原子、 氰基、 具有 1-40个 C原子的直链或带支 链的烷基或烷氧基、 或者芳基或杂芳基； R3选自 d-Czo的烷基；
n为自然数， 且 l < n≤100; m为自然数， 且 l < m≤20; x、 y为正实数 值， 且 x+y=l。
2、 根据权利要求 1 所述的有机半导体材料， 其特征在于， 、 R2 选自具有 1-18个 C原子的直链或带支链的烷基或烷氧基。
3、 根据权利要求 1 所述的有机半导体材料， 其特征在于， R3选自 C6-C17的烷基。
4、 根据权利要求 1所述的有机半导体材料， 其特征在于， m的取值 范围为 6≤m≤12。
5、 一种如权利要求 1至 4任一所述的有机半导体材料的制备方法， 其特征在于， 该制备方法包括如下步骤：
51、 无水无氧环境下， 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 ~ 1 :4加入至第一溶剂中溶解，然后加入 2-异丙氧基 -4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷或者双频哪醇合二硼， 升温到 20~30°C , 反应 12 - 48小时， 得到 2, 7-双（4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷基 ) - 9, 9-二坑基芴；
52、 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， 以及咔唑或其衍生物， 以摩尔比 m:j:k, 且 m=j+k, 加入到含有催化剂和碱溶液的第二溶剂中， 在 70°C ~ 100°C下进 行 Suzuki反应 24 ~ 72小时， 得到所述有机半导体材料。
6、 根据权利要求 5所述的有机半导体材料的制备方法，其特征在于， S1步骤中， 所述第一溶剂为四氢呋喃、 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 的摩尔用量为所述 2, 7-二溴 -9, 9-二烷基芴摩尔用量的 2 ~ 4倍。
7、 根据权利要求 5所述的有机半导体材料的制备方法，其特征在于， 所述 S2步骤中， 所述第二溶剂为苯、 氯苯、 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。
8、 根据权利要求 5或 7所述的有机半导体材料的制备方法， 其特征 在于， S2步骤中，
所述催化剂为有机钯或有机钯与有机碑配体的混合物； 所述催化剂的 用量为所述 2,7-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基 -9,9-二烷基芴摩尔 用量的 0.0005 0.2倍；
所述碱溶液为 NaOH水溶液、 Na2C03水溶液、 NaHC03水溶液或四乙 基氢氧化铵水溶液中的至少一种； 所述碱溶液中碱的摩尔用量为所述 2, 7- 双（4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷基） - 9, 9-二烷基硅芴摩尔用量的 2-20倍。
9、 根据权利要求 8所述的有机半导体材料的制备方法，其特征在于， 所述有机钯为 Pd(PPh3)4、 Pd(OAc)2、 Pd2(dba)3或 Pd(PPh3)2Cl2; 所述有机磷 配体为三环己基膦、 P(o-Tol)3 ; 所述有机钯与有机磷配体的混合物为 Pd2(dba)3/P(o-Tol)3。
10、 一种如权利要求 1至 4任一所述的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， 有机光存储， 有机非线性 材料或有机激光器件等领域中的应用。
PCT/CN2010/080012 2010-12-20 2010-12-20 一种有机半导体材料及其制备方法和应用 WO2012083515A1 (zh)

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