WO2016015533A1 - Organic small molecular semiconductor material, and synthetic method and use thereof - Google Patents

Organic small molecular semiconductor material, and synthetic method and use thereof Download PDF

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WO2016015533A1
WO2016015533A1 PCT/CN2015/082416 CN2015082416W WO2016015533A1 WO 2016015533 A1 WO2016015533 A1 WO 2016015533A1 CN 2015082416 W CN2015082416 W CN 2015082416W WO 2016015533 A1 WO2016015533 A1 WO 2016015533A1
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linear
semiconductor material
small molecule
organic small
molecule semiconductor
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武建昌
马玉超
王立磊
马昌期
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深圳市博世知识产权运营有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

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  • the present invention relates to a linear oligothiophene organic small molecule semiconductor material, a process for its preparation, and use thereof, for example, in a photosensitive device.
  • Organic semiconductor materials have the advantages of light weight, low production cost and easy large-area production, making the design and synthesis of organic semiconductor materials an important technology in the field of organic electronics.
  • the flexibility of organic semiconductor materials has greatly reduced the cost of production and transportation. Lay the foundation for personalized electronics.
  • Organic semiconductor materials can be classified into electron-donating materials and electron-accepting materials according to their use in organic electrons. Among them, electronic materials have developed very fast in recent years, and many high-performance organic electron donor semiconductor materials have emerged, such as poly(3-hexylthiophene) (P3HT), dithienobenzene-thiazino[3,4-b].
  • P3HT poly(3-hexylthiophene)
  • dithienobenzene-thiazino[3,4-b] such as poly(3-hexylthiophene) (P3HT), dithienobenzene-thiazino[3,4-b].
  • the main object of the present invention is to provide a novel organic small molecule semiconductor material which is easy to prepare, low in cost, and has strong electron accepting ability and high light absorbing ability.
  • Another object of the present invention is to provide a method of preparing the organic small molecule semiconductor material.
  • An organic small molecule semiconductor material comprising a diarylcyclopentadiene ⁇ -conjugated unit and an aromatic group, and having the following structural formula:
  • X 1 , X 2 are independently selected from O, S or Se
  • X 3 is selected from O, S, Se, NR 2 , C(R 2 ) 2 or Si(R 2 ) 2
  • R 2 is selected from C-containing numbers a linear or branched alkyl group of 1-20, a linear or branched modified alkylaryl or heterocyclic aryl group having a C number of 7-20
  • R1 is selected from a hydrogen atom and has a C number of 1-20.
  • A is an electron withdrawing unit (may also be named as a terminal electron withdrawing unit) , strong electrons, electron acceptor units, etc.).
  • a method for synthesizing an organic small molecule semiconductor material comprising: providing a first compound comprising a diarylcyclo and cyclopentadienyl ⁇ conjugated unit and a second compound comprising an aromatic group, which are obtained by a transition metal catalyzed condensation reaction The organic small molecule semiconductor material.
  • the organic small molecule semiconductor material can be applied to the preparation of organic electronic devices, particularly organic electronic devices having photo-electric conversion properties, such as organic thin film solar cells.
  • the present invention has at least the following advantages compared with the prior art:
  • the organic small molecule semiconductor material has strong electron-trapping chain length and short conjugate chain length, and is highly electron-accepting.
  • the lowest empty orbital level (LUMO) is about -3.8eV, which is more conjugated than most.
  • the lowest empty orbital energy level (LUMO) of the polymer donor material is at least 0.2 eV, which can be used as electron transfer between the electron acceptor and the conjugated polymer, and also has a smaller spectral band gap and strong light absorption capability. It is strong for the absorption of long-wavelength visible light;
  • the organic small molecule semiconductor material is easy to prepare, in particular, the synthesis and purification process is simple and the cost is low.
  • Figure 1-3 shows the synthetic route of the organic small molecule semiconductor material in the embodiment 1-3 of the present invention, respectively.
  • 4a-4b are molecular structural formulas of typical organic small molecule semiconductor materials F and G in the present invention.
  • Figure 5 is a view showing the ultraviolet-visible absorption spectrum of a typical organic small molecule semiconductor material D, F, G in the present invention.
  • 6, 7a, 7b are electrochemical spectra of typical organic small molecule semiconductor materials D, F, G in the present invention.
  • Embodiment 8 is a schematic structural view of an organic photoelectric device in Embodiment 7 of the present invention.
  • Figure 9 is an I-V test chart of the organic photovoltaic device shown in Figure 8.
  • an aspect of the present invention provides a novel organic small molecule semiconductor material comprising a diarylcyclopentadiene ⁇ -conjugated unit, directly bonded to a diaryl ring and a cyclopentadiene ⁇
  • the aromatic group on the conjugated unit and the electron withdrawing unit (strongly charged electron group) attached to the aromatic group are short conjugated chain small molecule compounds having a small volume.
  • the organic small molecule semiconductor acceptor material by introducing a strong electron withdrawing group and reducing the length of the conjugated chain (for example, five conjugated aromatic groups), the electron accepting ability and the long wavelength can be increased.
  • the absorption capacity of visible light can solve the problems of insufficient absorption and high price of existing electronic materials.
  • the organic small molecule semiconductor material of the present invention may have the following structural formula:
  • X1, X2 are independently selected from O, S or Se
  • X3 is selected from the group consisting of O, S, Se, NR 2 , C(R 2 ) 2 , Si(R 2 ) 2
  • R 2 is selected from the group consisting of C number 1 a linear or branched alkyl group of -20, a linear or branched modified alkaryl or heterocyclic aryl group having a C number of 7 to 20
  • R1 is selected from a hydrogen atom and having a C number of 1 to 20
  • X 1 is S, that is, the di-arylcyclopentadienyl ⁇ conjugated unit may have the following structure:
  • X 3 is Si(R 2 ) 2 , that is, the di-arylcyclopentadienyl ⁇ -conjugated unit may have the following structure:
  • the organic small molecule semiconductor material which can be considered as a linear oligothiophene
  • a charge transfer state can be further formed in the molecule, and the absorption spectrum of the material is red-shifted to increase the material.
  • the electron-withdrawing unit (electron acceptor unit) A may have at least one of the following structural formulas:
  • R 3 may be selected from H, a linear or branched alkyl group having a C number of 1 to 20, and a linear or branched modified alkaryl or heterocyclic aryl group having a C number of 7 to 20.
  • the electron withdrawing unit may preferably have any one of the following structural formulas:
  • R 3 is selected from the group consisting of H, a linear or branched alkyl group having a C number of 1 to 20, and a linear or branched modified alkaryl or heterocyclic aryl group having a C number of 7 to 20.
  • Another aspect of the present invention provides a method for synthesizing an organic small molecule semiconductor material, comprising: providing a first compound comprising a diarylcyclo and cyclopentadienyl ⁇ -conjugated unit and a second compound comprising an aromatic group,
  • the organic small molecule semiconductor material is obtained by a transition metal catalyzed condensation reaction.
  • first compound may have the following structural formula:
  • X 1 and X 2 are independently selected from O, S or Se
  • X 3 is selected from O, S, Se, NR 2 , C(R 2 ) 2 or Si(R 2 ) 2
  • X 4 and X 5 are independently selected.
  • R 1 is selected from a linear or branched alkyl group having a C number of 1 to 20, a linear or branched alkylaryl group or a heterocyclic aryl group having a C number of 7 to 20, and R 4 is selected.
  • a linear or branched alkyl group having a C number of from 1 to 4 R 5 is selected from a hydrogen atom, a linear or branched alkyl group having a C number of from 1 to 4, and A is an electron withdrawing unit.
  • X 4 or X 5 may be selected from substituted units having the following chemical formula:
  • two R 5 units may also be linked and form a 5-7 membered cyclic substituted or unsubstituted boron ester with an adjacent OBO.
  • transition metal catalyzed condensation reaction may be selected from a metal catalyzed Suzuki condensation or a metal catalyzed Stille condensation reaction.
  • the synthetic route of the organic small molecule semiconductor material can be as follows:
  • X1, X2 are independently selected from O, S, Se, and X3 is selected from the group consisting of O, S, Se, NR 2 , C(R 2 ) 2 , Si(R 2 ) 2 , wherein R 4 is selected from the group consisting of C number a linear or branched alkyl group of 1 to 20, and R 2 is selected from a linear or branched alkyl group having a C number of 1 to 20, and a linear or branched modified alkylaryl group having a C number of 7 to 20 Or a heterocyclic aryl group, R1 is selected from a hydrogen atom, a linear or branched alkyl group having a C number of 1 to 20, and a linear or branched modified alkylaryl or heterocyclic aromatic group having a C number of 7 to 20 Base, A is an electron withdrawing unit (terminal electron withdrawing unit).
  • Typical examples of the organic small molecule semiconductor material in the present invention can be referred to the product B in Fig. 1, the product D in Figs. 2-3, and the compounds F and G shown in Figs. 4a to 4b.
  • the organic semiconductor material synthesized by the invention has a small molecular conjugation length, and has a strong terminal electron-trapping group in the molecule, and the highest occupied orbital (HOMO) and the lowest empty orbital level of the series of molecules. (LUMO) is lower and thus more suitable as an electron acceptor material.
  • the molecular frontier orbital energy level can be determined by suitable means known in the art, such as electrochemical cyclic voltammetry.
  • Yet another aspect of the invention provides the use of any of the foregoing organic small molecule semiconductor materials, for example, in the preparation of organic electronic devices.
  • the organic small molecule semiconductor material provided by the invention has low lowest occupied orbit (HOMO) and lowest empty orbital level (LUMO), and can be used as an electron acceptor material and an organic electronic device. in.
  • HOMO lowest occupied orbit
  • LUMO lowest empty orbital level
  • the organic small molecular semiconductor material and the conjugated polymer can be utilized An organic small molecule semiconductor-conjugated polymer composite is formed and used to prepare an organic electronic device.
  • the highest molecular occupying orbital energy level of the conjugated polymer is at least 0.2 eV higher than the highest molecular orbital energy level of the organic small molecular semiconductor material.
  • the lowest molecular empty orbital energy level of the conjugated polymer is at least 0.2 eV higher than the lowest molecular empty orbital energy level of the organic small molecular semiconductor material, so that effective charge transfer can occur between the formed composites. Forming a charge separation state.
  • the complex described in the present invention can be formed into a liquid by dissolving the organic small molecule and the conjugated polymer provided by the present invention together in an organic solvent.
  • the organic solvent may be selected from, but not limited to, chloroform, trichloroethane, tetrachloroethane, tetrahydrofuran, chlorobenzene, dichlorobenzene, a mixed solvent formed of two or more of them, and the like. Further, such a composite may contain other additives such as metal oxide nanoparticles, 1,8-diiodoolane, etc., but is not limited thereto.
  • the conjugated polymer may be at least selected from the group consisting of poly(3-hexylthiophene) (P3HT), a copolymer of dithienobenzene-thiato[3,4-b]thiophene (PTB7), poly[2, 6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']bisthiophene)-alternating 4,7-(2,1,3 - benzothiadiazole)] (PCPDTBT), but is not limited thereto. 6, please refer to FIG.
  • a thin film can also be prepared using the organic small molecule semiconductor material or the organic small molecule semiconductor-conjugated polymer composite.
  • the method for preparing the film may be selected from a suitable method known in the art such as spin coating, ink jet printing, screen printing, and the like.
  • the organic small molecule semiconductor material, the organic small molecule semiconductor-conjugated polymer composite or the thin film can also be used to prepare an organic electronic device, in particular, having photo-electric conversion properties.
  • Organic electronic devices such as organic thin film solar cells.
  • the synthetic preparation process of the organic small molecule semiconductor material may be:
  • the synthetic preparation process of the organic small molecule semiconductor material may be:
  • the synthetic preparation process of the organic small molecule semiconductor material may be: starting material E (200 mg, 274 ⁇ mol), raw material A (222 mg, 685 ⁇ mol) added to a 100 ml single-neck round bottom flask, tetrakis(triphenylphosphine) Palladium (17 mg, 14.7 ⁇ mol) was added to the reactor under nitrogen, and the fully degassed dimethylformamide (DMF) (23 ml) was added to the reactor and stirred at 60 ° C for about 6 hours. After the reaction, it was washed with water and separated. , combining organic phases. The organic phase was dried over anhydrous sodium sulfate, and then evaporated and evaporated, and then evaporated.
  • starting material E 200 mg, 274 ⁇ mol
  • raw material A 222 mg, 685 ⁇ mol
  • tetrakis(triphenylphosphine) Palladium 17 mg, 14.7 ⁇ mol
  • DMF fully degassed dimethylformamide
  • Example 4 The electrochemical properties of the organic small molecule semiconductor material of the present invention can be tested by cyclic voltammetry or the like.
  • the small molecular semiconductor material F as an example, it can be dissolved in anhydrous dichloromethane, and a bias voltage (-1.8 volt - 1.8 volt) is applied to obtain a cyclic voltammetry curve.
  • a small amount of ferrocene was added to the anhydrous dichloromethane solution of F to test the cyclic voltammetry curve of ferrocene.
  • the redox potential of the small molecule semiconductor material relative to ferrocene is obtained (see Fig. 7a).
  • the highest molecular occupied orbital level (HOMO) and the lowest molecular empty orbital level (LUMO) of a small molecule semiconductor material can be calculated by the following formula:
  • E LUMO -(E red onset +5.10)(eV)
  • E ox onset is the initial oxidation potential and E red onset is the initial reduction potential.
  • Example 5 A typical organic small molecule-conjugated polymer composite can be prepared by: poly(3-hexylthiophene) (P3HT) and small molecular semiconductor material F 5 mg each, adding 1 ml of chlorobenzene at 50 Stir at 90 ° C for 10 hours.
  • P3HT poly(3-hexylthiophene)
  • F 5 mg small molecular semiconductor material
  • Example 6 Preparation of a composite film by a spin coating method: A film of the composite solution of Example 5 was rotated at 600 rpm for 1 minute to prepare a film having a film thickness of about 80 nm.
  • Embodiment 7 Please refer to FIG. 8 is an organic photovoltaic device constructed by using an organic small molecule semiconductor material of the present invention, which may be disposed on a substrate, including an indium tin oxide layer (ITO), a hole transport layer, and an organic a photosensitive layer, an electron transport layer and a contact electrode, wherein the materials of each layer may be ITO, PEDOT: PSS, P3HT: F, PFN, Al, wherein PEDOT: PSS is poly(3,4-ethylenedioxythiophene) and a mixture of polystyrene sulfonates, P3HT is poly(3-hexylthiophene), F is typical in the present invention.
  • the small molecule semiconductor material F (Fig.
  • PFN poly[9,9-dioctylindole-9,9-bis(N,N-dimethylaminopropyl) fluorene].
  • the organic small molecule semiconductor material of the invention has a small spectral band gap, a long spectral absorption wavelength, a lower highest occupied orbit and a lowest empty orbital level, and can be used as a photovoltaic material, especially in organic photovoltaics.
  • Receptor material and it also has the advantages of simple preparation process, low cost and the like.

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Abstract

Disclosed are an organic small molecular semiconductor material, and a synthetic method therefor. The semiconductor material comprises a diaromatic ring pentalene π-conjugate unit and an aromatic group, and has the following structural formula (I), wherein X1 and X2 are independently selected from O, S or Se; X3 is selected from O, S, Se, NR2, C(R2)2 or Si(R2)2; R2 is selected from a linear or branched alkyl group comprising 1-20 carbon atoms, and a linear or branched modified alkaryl or heterocyclic aryl comprising 7-20 carbon atoms; R1 is selected from a hydrogen atom, a linear or branched alkyl group comprising 1-20 carbon atoms, and a linear or branched modified alkaryl or heterocyclic aryl comprising 7-20 carbon atoms; and A is an electron-withdrawing unit. The semiconductor material can be synthesised by a transition metal catalysed condensation reaction. The semiconductor material of the present invention has a small spectrum band gap, a long spectrum absorption wavelength, a relatively low highest occupied molecular orbital and lowest unoccupied molecular orbital energy level, and can be used as a photoelectric material, especially as a receptor material in an organic photovoltaic device, and it also has advantages such as a simple preparation process, a low cost, etc.

Description

有机小分子半导体材料、其合成方法及应用Organic small molecule semiconductor material, synthesis method and application thereof 技术领域Technical field
本发明特别涉及一种线性寡聚噻吩有机小分子半导体材料、其制备方法及用途，例如在光敏器件中的应用。More particularly, the present invention relates to a linear oligothiophene organic small molecule semiconductor material, a process for its preparation, and use thereof, for example, in a photosensitive device.
背景技术Background technique
有机半导体材料具有质量轻、生产成本低和易于大面积生产等优点，使得有机半导体材料设计及合成成为有机电子领域内的重要技术，有机半导体材料的柔性化，使其生产和运输成本大大降低，为个性化的电子器件打下基础。Organic semiconductor materials have the advantages of light weight, low production cost and easy large-area production, making the design and synthesis of organic semiconductor materials an important technology in the field of organic electronics. The flexibility of organic semiconductor materials has greatly reduced the cost of production and transportation. Lay the foundation for personalized electronics.
有机半导体材料按照其在有机电子中的用途可分为给电子材料和受电子材料。其中给电子材料近几年发展非常快，已经出现许多高性能有机电子给体半导体材料，如：聚(3-己基噻吩)(P3HT)、二噻吩并苯-噻并[3,4-b]噻吩的共聚物(PTB7)、聚[2,6-(4,4-双-(2-乙基己基)-4H-环戊[2,1-b；3,4-b’]双噻吩)-交替4,7-(2,1,3-苯并噻二唑)](PCPDTBT)，DCV5T-Me,DR3TBDTT等。这些材料作用在有机光伏器件中(参阅AdvancedFunctionalMaterials 2008,18(20),3323-3331.Nature photonics 2012,6,591-595.Advanced Functional Materials 2008,18(12),1757-1766.)，其光电转换效率达到9％以上，接近商业化生产所需效率。然而，受电子材料发展相对缓慢，在有机光伏器件中最常用的是富勒烯衍生物。富勒烯衍生物在可见光范围内的吸收非常弱，而且其合成和纯化过程比较复杂使得其价格很高，增加了有机光伏器件的成本。Organic semiconductor materials can be classified into electron-donating materials and electron-accepting materials according to their use in organic electrons. Among them, electronic materials have developed very fast in recent years, and many high-performance organic electron donor semiconductor materials have emerged, such as poly(3-hexylthiophene) (P3HT), dithienobenzene-thiazino[3,4-b]. Copolymer of thiophene (PTB7), poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']bisthiophene) - Alternate 4,7-(2,1,3-benzothiadiazole)] (PCPDTBT), DCV5T-Me, DR3TBDTT, and the like. These materials act on organic photovoltaic devices (see Advanced Functional Materials 2008, 18(20), 3323-3331. Nature photonics 2012, 6, 591-595. Advanced Functional Materials 2008, 18(12), 1757-1766.), their photoelectric conversion efficiency More than 9%, close to the efficiency required for commercial production. However, electronic materials are relatively slow to develop, and the most commonly used in organic photovoltaic devices are fullerene derivatives. Fullerene derivatives absorb very little in the visible range, and their synthesis and purification processes are complex, making them expensive and increasing the cost of organic photovoltaic devices.
发明内容Summary of the invention
针对现有技术的不足，本发明的主要目的在于提供一种易于制备，成本低廉，且具有较强受电子能力和较高光吸收能力的新型有机小分子半导体材料。In view of the deficiencies of the prior art, the main object of the present invention is to provide a novel organic small molecule semiconductor material which is easy to prepare, low in cost, and has strong electron accepting ability and high light absorbing ability.
本发明的另一目的在于提供一种制备所述有机小分子半导体材料的方法。Another object of the present invention is to provide a method of preparing the organic small molecule semiconductor material.
本发明的又一目的在于提供所述有机小分子半导体材料的用途。 It is still another object of the present invention to provide the use of the organic small molecule semiconductor material.
为实现前述发明目的，本发明采用的技术方案如下：In order to achieve the foregoing object, the technical solution adopted by the present invention is as follows:
一种有机小分子半导体材料，包含二芳环并环戊二烯类π共轭单元及芳香基团，并具有如下结构式：An organic small molecule semiconductor material comprising a diarylcyclopentadiene π-conjugated unit and an aromatic group, and having the following structural formula:
Figure PCTCN2015082416-appb-000001
Figure PCTCN2015082416-appb-000001
其中X1、X2独立地选自O、S或Se，X3选自O、S、Se、NR2、C(R2)2或Si(R2)2，R2选自含C数为1-20的直链或支链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，R1选自氢原子、含C数为1-20的直链或支链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，A为吸电子单元(亦可命名为端位拉电子基团单元、强拉电子基、电子受体单元等等)。Wherein X 1 , X 2 are independently selected from O, S or Se, X 3 is selected from O, S, Se, NR 2 , C(R 2 ) 2 or Si(R 2 ) 2 , and R 2 is selected from C-containing numbers a linear or branched alkyl group of 1-20, a linear or branched modified alkylaryl or heterocyclic aryl group having a C number of 7-20, and R1 is selected from a hydrogen atom and has a C number of 1-20. a linear or branched alkyl group, a linear or branched modified alkylaryl or heterocyclic aryl group having a C number of 7 to 20, and A is an electron withdrawing unit (may also be named as a terminal electron withdrawing unit) , strong electrons, electron acceptor units, etc.).
一种有机小分子半导体材料的合成方法，包括：提供包含二芳环并环戊二烯类π共轭单元的第一化合物与包含芳香基团的第二化合物，经过渡金属催化缩合反应，获得所述有机小分子半导体材料。A method for synthesizing an organic small molecule semiconductor material, comprising: providing a first compound comprising a diarylcyclo and cyclopentadienyl π conjugated unit and a second compound comprising an aromatic group, which are obtained by a transition metal catalyzed condensation reaction The organic small molecule semiconductor material.
所述有机小分子半导体材料可应用于制备有机电子器件，特别是具有光-电转换特性的有机电子器件，例如有机薄膜太阳能电池。The organic small molecule semiconductor material can be applied to the preparation of organic electronic devices, particularly organic electronic devices having photo-electric conversion properties, such as organic thin film solar cells.
由于以上技术方案的实施，使得本发明与现有技术相比至少具有如下优点：Due to the implementation of the above technical solutions, the present invention has at least the following advantages compared with the prior art:
(1)该有机小分子半导体材料因具有强的拉电子基团和较短的共轭链长，受电子能力强，最低空轨道能级(LUMO)在-3.8eV左右，较大多数共轭聚合物给体材料的最低空轨道能级(LUMO)高至少0.2eV，能够作为电子受体与共轭聚合物之间发生电子转移，且还具有更小的光谱带隙，光吸收能力强，特别是对于长波长的可见光的吸收能力强；(1) The organic small molecule semiconductor material has strong electron-trapping chain length and short conjugate chain length, and is highly electron-accepting. The lowest empty orbital level (LUMO) is about -3.8eV, which is more conjugated than most. The lowest empty orbital energy level (LUMO) of the polymer donor material is at least 0.2 eV, which can be used as electron transfer between the electron acceptor and the conjugated polymer, and also has a smaller spectral band gap and strong light absorption capability. It is strong for the absorption of long-wavelength visible light;
(2)该有机小分子半导体材料易于制备，特别是其合成及提纯工艺简单，成本低廉。(2) The organic small molecule semiconductor material is easy to prepare, in particular, the synthesis and purification process is simple and the cost is low.
附图说明DRAWINGS
图1-3所示分别是本发明实施例1-3中有机小分子半导体材料的合成路线 图；Figure 1-3 shows the synthetic route of the organic small molecule semiconductor material in the embodiment 1-3 of the present invention, respectively. Figure
图4a-图4b是本发明中典型有机小分子半导体材料F、G的分子结构式；4a-4b are molecular structural formulas of typical organic small molecule semiconductor materials F and G in the present invention;
图5所示是本发明中典型有机小分子半导体材料D、F、G的紫外-可见吸收光谱图；Figure 5 is a view showing the ultraviolet-visible absorption spectrum of a typical organic small molecule semiconductor material D, F, G in the present invention;
图6、图7a、图7b所示是本发明中典型有机小分子半导体材料D、F、G的电化学图谱；6, 7a, 7b are electrochemical spectra of typical organic small molecule semiconductor materials D, F, G in the present invention;
图8是本发明实施例7中的一种有机光电器件的结构示意图；8 is a schematic structural view of an organic photoelectric device in Embodiment 7 of the present invention;
图9是图8所示有机光伏器件的I-V测试图。Figure 9 is an I-V test chart of the organic photovoltaic device shown in Figure 8.
具体实施方式detailed description
鉴于现有技术的诸多缺陷，本案发明人经长期研究和大量实践，得以提出本发明的技术方案。In view of the many shortcomings of the prior art, the inventors of the present invention have been able to propose the technical solution of the present invention through long-term research and extensive practice.
进一步的讲，本发明的一个方面提供了一种新型的有机小分子半导体材料，其包含二芳环并环戊二烯类π共轭单元、直接连接在二芳环并环戊二烯类π共轭单元上的芳香基团以及连接在芳香基团上的吸电子单元(强拉电子基)，系体积很小的短共轭链小分子化合物。Further, an aspect of the present invention provides a novel organic small molecule semiconductor material comprising a diarylcyclopentadiene π-conjugated unit, directly bonded to a diaryl ring and a cyclopentadiene π The aromatic group on the conjugated unit and the electron withdrawing unit (strongly charged electron group) attached to the aromatic group are short conjugated chain small molecule compounds having a small volume.
该有机小分子半导体受体材料中，通过引入强的吸电子基团，并减小共轭链长度(例如，五个共轭芳香基团)，可以增加其受电子能力和和对长波长的可见光的吸收能力，从而解决现有受电子材料吸光不足、价格昂贵等问题。In the organic small molecule semiconductor acceptor material, by introducing a strong electron withdrawing group and reducing the length of the conjugated chain (for example, five conjugated aromatic groups), the electron accepting ability and the long wavelength can be increased. The absorption capacity of visible light can solve the problems of insufficient absorption and high price of existing electronic materials.
作为较为优选的实施方案之一，本发明的有机小分子半导体材料可以具有如下结构式：As one of the more preferred embodiments, the organic small molecule semiconductor material of the present invention may have the following structural formula:
Figure PCTCN2015082416-appb-000002
Figure PCTCN2015082416-appb-000002
其中X1、X2独立地选自O、S或Se，X3选自O、S、Se、NR2，C(R2)2，Si(R2)2，其中R2选自含C数为1-20的直链或支链烷基，含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，R1选自氢原子、含C数为1-20的直链或支 链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，A为端位拉电子基团单元。Wherein X1, X2 are independently selected from O, S or Se, and X3 is selected from the group consisting of O, S, Se, NR 2 , C(R 2 ) 2 , Si(R 2 ) 2 , wherein R 2 is selected from the group consisting of C number 1 a linear or branched alkyl group of -20, a linear or branched modified alkaryl or heterocyclic aryl group having a C number of 7 to 20, and R1 is selected from a hydrogen atom and having a C number of 1 to 20 A chain or branched alkyl group, a linear or branched modified alkaryl or heterocyclic aryl group having a C number of 7 to 20, and A is a terminal electron withdrawing unit.
在一较佳案例中，X1为S，即所述二芳环并环戊二烯类π共轭单元可具有以下结构：In a preferred embodiment, X 1 is S, that is, the di-arylcyclopentadienyl π conjugated unit may have the following structure:
Figure PCTCN2015082416-appb-000003
Figure PCTCN2015082416-appb-000003
在一较佳案例中，X3为Si(R2)2，即所述二芳环并环戊二烯类π共轭单元还可具有以下结构：In a preferred embodiment, X 3 is Si(R 2 ) 2 , that is, the di-arylcyclopentadienyl π-conjugated unit may have the following structure:
Figure PCTCN2015082416-appb-000004
Figure PCTCN2015082416-appb-000004
进一步的，通过在有机小分子半导体材料(可认为是线性寡聚噻吩)的两个端位引入吸电子单元，可以还使分子内形成电荷转移态，红移该材料的吸收光谱，增加该材料的受电子能力。Further, by introducing an electron withdrawing unit at both end positions of the organic small molecule semiconductor material (which can be considered as a linear oligothiophene), a charge transfer state can be further formed in the molecule, and the absorption spectrum of the material is red-shifted to increase the material. The ability to accept electronics.
其中，吸电子单元(电子受体单元)A至少可具有下列结构式中的任一种：Wherein, the electron-withdrawing unit (electron acceptor unit) A may have at least one of the following structural formulas:
Figure PCTCN2015082416-appb-000005
Figure PCTCN2015082416-appb-000005
其中，R3可选自H、含C数为1-20的直链或支链烷基，含C数为7-20的直链或支链修饰的烷芳基或杂环芳基。Wherein R 3 may be selected from H, a linear or branched alkyl group having a C number of 1 to 20, and a linear or branched modified alkaryl or heterocyclic aryl group having a C number of 7 to 20.
进一步的，所述吸电子单元可优选具有下列结构式中的任一者： Further, the electron withdrawing unit may preferably have any one of the following structural formulas:
Figure PCTCN2015082416-appb-000006
Figure PCTCN2015082416-appb-000006
其中，R3选自H、含C数为1-20的直链或支链烷基，含C数为7-20的直链或支链修饰的烷芳基或杂环芳基。Wherein R 3 is selected from the group consisting of H, a linear or branched alkyl group having a C number of 1 to 20, and a linear or branched modified alkaryl or heterocyclic aryl group having a C number of 7 to 20.
本发明的另一个方面提供了一种有机小分子半导体材料的合成方法，包括：提供包含二芳环并环戊二烯类π共轭单元的第一化合物与包含芳香基团的第二化合物，经过渡金属催化缩合反应，获得所述有机小分子半导体材料。Another aspect of the present invention provides a method for synthesizing an organic small molecule semiconductor material, comprising: providing a first compound comprising a diarylcyclo and cyclopentadienyl π-conjugated unit and a second compound comprising an aromatic group, The organic small molecule semiconductor material is obtained by a transition metal catalyzed condensation reaction.
其中，所述第一化合物可具有如下结构式：Wherein the first compound may have the following structural formula:
Figure PCTCN2015082416-appb-000007
Figure PCTCN2015082416-appb-000007
其中，所述第二化合物可具有如下结构式：Wherein the second compound may have the following structural formula:
Figure PCTCN2015082416-appb-000008
Figure PCTCN2015082416-appb-000008
其中，X1、X2独立地选自O、S或Se，X3选自O、S、Se、NR2、C(R2)2或Si(R2)2，X4、X5独立地选自卤素原子、Sn(R4)3、BO(R5)2或包含-O-B-O-的5-7元环状取代或未取代的硼酯，且X4、X5之中有且只有一个为卤素原子，R1选自含C数为1-20的直链或支链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，R4选自含C数为1-4的直链或支链烷基，R5选自氢原子、C数为1-4的直链或支链烷基，A为吸电子单元。Wherein X 1 and X 2 are independently selected from O, S or Se, and X 3 is selected from O, S, Se, NR 2 , C(R 2 ) 2 or Si(R 2 ) 2 , and X 4 and X 5 are independently selected. Is selected from a halogen atom, Sn(R 4 ) 3 , BO(R 5 ) 2 or a 5-7 membered cyclic substituted or unsubstituted boron ester containing -OBO-, and one and only one of X4 and X5 is a halogen atom, R 1 is selected from a linear or branched alkyl group having a C number of 1 to 20, a linear or branched alkylaryl group or a heterocyclic aryl group having a C number of 7 to 20, and R 4 is selected. A linear or branched alkyl group having a C number of from 1 to 4, R 5 is selected from a hydrogen atom, a linear or branched alkyl group having a C number of from 1 to 4, and A is an electron withdrawing unit.
进一步的，X4或X5可以选自具有如下化学通式的取代单元：Further, X 4 or X 5 may be selected from substituted units having the following chemical formula:
Figure PCTCN2015082416-appb-000009
Figure PCTCN2015082416-appb-000009
其中，两个R5单元还可相连并与相邻的O-B-O形成5-7元环状取代或未取代的硼酯。 Among them, two R 5 units may also be linked and form a 5-7 membered cyclic substituted or unsubstituted boron ester with an adjacent OBO.
进一步的，所述过渡金属催化缩合反应可选自金属催化Suzuki缩合或金属催化Stille缩合反应。Further, the transition metal catalyzed condensation reaction may be selected from a metal catalyzed Suzuki condensation or a metal catalyzed Stille condensation reaction.
在一些具体实施案例中，该有机小分子半导体材料的合成路线可如下式所示：In some specific embodiments, the synthetic route of the organic small molecule semiconductor material can be as follows:
Figure PCTCN2015082416-appb-000010
Figure PCTCN2015082416-appb-000010
其中，X1，X2独立地选自O、S、Se，X3选自O、S、Se、NR2，C(R2)2，Si(R2)2，其中R4选自含C数为1-20的直链或支链烷基，R2选自含C数为1-20的直链或支链烷基，含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，R1选自氢原子、含C数为1-20的直链或支链烷基，含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，A为吸电子单元(端位拉电子基团单元)。Wherein X1, X2 are independently selected from O, S, Se, and X3 is selected from the group consisting of O, S, Se, NR 2 , C(R 2 ) 2 , Si(R 2 ) 2 , wherein R 4 is selected from the group consisting of C number a linear or branched alkyl group of 1 to 20, and R 2 is selected from a linear or branched alkyl group having a C number of 1 to 20, and a linear or branched modified alkylaryl group having a C number of 7 to 20 Or a heterocyclic aryl group, R1 is selected from a hydrogen atom, a linear or branched alkyl group having a C number of 1 to 20, and a linear or branched modified alkylaryl or heterocyclic aromatic group having a C number of 7 to 20 Base, A is an electron withdrawing unit (terminal electron withdrawing unit).
本发明中有机小分子半导体材料的典型样例可参照图1中的产品B、图2-3中的产品D、图4a-图4b所示的化合物F和G。Typical examples of the organic small molecule semiconductor material in the present invention can be referred to the product B in Fig. 1, the product D in Figs. 2-3, and the compounds F and G shown in Figs. 4a to 4b.
本发明所合成的有机半导体材分子中具有较小的分子共轭长度，同时该分子中具有很强的端位拉电子基团，该系列分子的最高占据轨道(HOMO)及最低空轨道能级(LUMO)较低，因而更适宜作为电子受体材料。分子前线轨道能级可以利用业界所知的合适方式，例如电化学循环伏安法测定。The organic semiconductor material synthesized by the invention has a small molecular conjugation length, and has a strong terminal electron-trapping group in the molecule, and the highest occupied orbital (HOMO) and the lowest empty orbital level of the series of molecules. (LUMO) is lower and thus more suitable as an electron acceptor material. The molecular frontier orbital energy level can be determined by suitable means known in the art, such as electrochemical cyclic voltammetry.
本发明又一个方面提供了前述任一种有机小分子半导体材料的用途，例如，在制备有机电子器件中的应用。Yet another aspect of the invention provides the use of any of the foregoing organic small molecule semiconductor materials, for example, in the preparation of organic electronic devices.
作为其中的应用方案之一，本发明提供的有机小分子半导体材料由于具有较低的最高占据轨道(HOMO)及最低空轨道能级(LUMO)，其可以作为电子受体材料应用与有机电子器件中。As one of the application schemes, the organic small molecule semiconductor material provided by the invention has low lowest occupied orbit (HOMO) and lowest empty orbital level (LUMO), and can be used as an electron acceptor material and an organic electronic device. in.
作为一个典型的应用，可利用所述有机小分子半导体材料与共轭聚合物复 合形成有机小分子半导体-共轭聚合物复合物，并利用其来制备有机电子器件。与本发明的有机小分子半导体材料作为与电子受体材料相匹配，所述共轭聚合物的最高分子占据轨道能级较所述有机小分子半导体材料的最高分子占据轨道能级高至少0.2eV，而所述共轭聚合物的最低分子空轨道能级较所述有机小分子半导体材料的最低分子空轨道能级高至少0.2eV，从而能够满足所形成的复合物之间能够发生有效电荷转移，形成电荷分离态。As a typical application, the organic small molecular semiconductor material and the conjugated polymer can be utilized An organic small molecule semiconductor-conjugated polymer composite is formed and used to prepare an organic electronic device. In combination with the organic small molecule semiconductor material of the present invention as an electron acceptor material, the highest molecular occupying orbital energy level of the conjugated polymer is at least 0.2 eV higher than the highest molecular orbital energy level of the organic small molecular semiconductor material. And the lowest molecular empty orbital energy level of the conjugated polymer is at least 0.2 eV higher than the lowest molecular empty orbital energy level of the organic small molecular semiconductor material, so that effective charge transfer can occur between the formed composites. Forming a charge separation state.
本发明中所述的复合物可以通过将本发明提供的有机小分子与共轭聚合物共同溶解在有机溶剂之中，形成液体状。所述的有机溶剂可选自但不限于氯仿、三氯乙烷、四氯乙烷、四氢呋喃、氯苯、二氯苯、或由他们中的两种或两种以上形成的混合溶剂等。又及，这种复合物中也可以包含其他添加剂，如：金属氧化物纳米颗粒、1,8-二碘葵烷等，但不限于此。The complex described in the present invention can be formed into a liquid by dissolving the organic small molecule and the conjugated polymer provided by the present invention together in an organic solvent. The organic solvent may be selected from, but not limited to, chloroform, trichloroethane, tetrachloroethane, tetrahydrofuran, chlorobenzene, dichlorobenzene, a mixed solvent formed of two or more of them, and the like. Further, such a composite may contain other additives such as metal oxide nanoparticles, 1,8-diiodoolane, etc., but is not limited thereto.
进一步的，所述共轭聚合物至少可选自聚(3-己基噻吩)(P3HT)、二噻吩并苯-噻并[3,4-b]噻吩的共聚物(PTB7)、聚[2,6-(4,4-双-(2-乙基己基)-4H-环戊[2,1-b；3,4-b’]双噻吩)-交替4,7-(2,1,3-苯并噻二唑)](PCPDTBT)中的任一种，但不限于此。其中，请参照图6，P3HT(HOMO＝-2.91eV,LUMO＝-5.06eV),PTB7(HOMO＝-3.31eV,LUMO＝-5.15eV),PCPDTBT(HOMO＝-3.55eV,LUMO＝-5.3eV)。Further, the conjugated polymer may be at least selected from the group consisting of poly(3-hexylthiophene) (P3HT), a copolymer of dithienobenzene-thiato[3,4-b]thiophene (PTB7), poly[2, 6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']bisthiophene)-alternating 4,7-(2,1,3 - benzothiadiazole)] (PCPDTBT), but is not limited thereto. 6, please refer to FIG. 6, P3HT (HOMO=-2.91eV, LUMO=-5.06eV), PTB7 (HOMO=-3.31eV, LUMO=-5.15eV), PCPDTBT (HOMO=-3.55eV, LUMO=-5.3eV) ).
作为其中的应用方案之一，还可利用所述有机小分子半导体材料或所述有机小分子半导体-共轭聚合物复合物制备一种薄膜。薄膜的制备方法可选自旋涂、喷墨印刷、丝网印刷等业界所知的适用方式。As one of the applications, a thin film can also be prepared using the organic small molecule semiconductor material or the organic small molecule semiconductor-conjugated polymer composite. The method for preparing the film may be selected from a suitable method known in the art such as spin coating, ink jet printing, screen printing, and the like.
作为其中的应用方案之一，还可利用所述有机小分子半导体材料、所述有机小分子半导体-共轭聚合物复合物或所述薄膜制备有机电子器件，特别是具有光-电转换特性的有机电子器件，例如有机薄膜太阳能电池。As one of the applications, the organic small molecule semiconductor material, the organic small molecule semiconductor-conjugated polymer composite or the thin film can also be used to prepare an organic electronic device, in particular, having photo-electric conversion properties. Organic electronic devices, such as organic thin film solar cells.
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行详细的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention are described in detail below with reference to the accompanying drawings in the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
实施例1参阅图1，该有机小分子半导体材料的合成制备工艺可以为： Embodiment 1 Referring to FIG. 1, the synthetic preparation process of the organic small molecule semiconductor material may be:
原料A(2.51g,7.77mmol)加入100ml单口圆底烧瓶瓶，在氮气环境下加入联硼酸频那醇酯(3.9g)、[1,1'-双(二苯基磷)二茂铁]二氯化钯(570mg)、醋酸钾(2.28g)、乙二醇二甲醚(55ml)。在70℃下搅拌反应10-15小时，反应结束后经过水洗，分液，合并有机相。有机相经过无水硫酸钠干燥，旋蒸除去有机溶液，粗产物用甲醇重结晶，得到最终产物B(2.11g)，收率75％。Starting material A (2.51 g, 7.77 mmol) was added to a 100 ml single-neck round bottom flask, and boranoic acid pinacol ester (3.9 g), [1,1'-bis(diphenylphosphino)ferrocene] was added under a nitrogen atmosphere. Palladium dichloride (570 mg), potassium acetate (2.28 g), ethylene glycol dimethyl ether (55 ml). The reaction was stirred at 70 ° C for 10-15 hours, washed with water after completion of the reaction, and the organic phases were combined. The organic phase was dried over anhydrous sodium sulfate and evaporated to dryness.
该产品B的表征数据如下：1H NMR(400MHz,CDCl3)δ＝7.76(s,1H),7.66(s,1H),2.90–2.78(m,2H),1.56(dd,J＝14.7,7.1Hz,2H),1.34(s,13H),1.32–1.27(m,6H),0.88(t,J＝6.7Hz,3H)。MS(EI):m/z＝370.2(M+)。The characterization data for this product B is as follows: 1 H NMR (400 MHz, CDCl 3 ) δ = 7.76 (s, 1H), 7.66 (s, 1H), 2.90 - 2.78 (m, 2H), 1.56 (dd, J = 14.7, 7.1 Hz, 2H), 1.34 (s, 13H), 1.32 - 1.27 (m, 6H), 0.88 (t, J = 6.7 Hz, 3H). MS (EI): m/z = 370.2 (M + ).
实施例2参阅图2，该有机小分子半导体材料的合成制备工艺可以为： Embodiment 2 Referring to FIG. 2, the synthetic preparation process of the organic small molecule semiconductor material may be:
原料B(50mg,135μmol),原料C(30mg,54μmol)加入25ml单口圆底烧瓶瓶，三(二亚苄基丙酮)二钯(7mg,6.75μmol)，四氟硼酸三叔丁基膦(3.9mg,13.5μmol)在氮气保护下加入反应器，经过充分脱气的四氢呋喃(3ml)加入反应器，搅拌使原料和催化剂溶解，碳酸钠溶液(0.81ml,1mol/L)滴入反应液，搅拌约2小时，反应结束后经过水洗，分液，合并有机相。有机相经过无水硫酸钠干燥，旋蒸除去有机溶液，薄板层析技术提纯，得到最终产品D(47.9mg)，收率74％。Starting material B (50 mg, 135 μmol), starting material C (30 mg, 54 μmol) was added to a 25 ml single-neck round bottom flask, tris(dibenzylideneacetone)dipalladium (7 mg, 6.75 μmol), tri-tert-butylphosphonium tetrafluoroborate (3.9 Mg, 13.5 μmol) was added to the reactor under nitrogen atmosphere, and the fully degassed tetrahydrofuran (3 ml) was added to the reactor, and the raw materials and the catalyst were dissolved by stirring, and sodium carbonate solution (0.81 ml, 1 mol/L) was dropped into the reaction solution, and stirred. After about 2 hours, after the end of the reaction, it was washed with water, separated, and the organic phases were combined. The organic phase was dried over anhydrous sodium sulfate, and then evaporated and evaporated.
该产品D的表征数据如下：1H NMR(400MHz,CDCl3)δ＝7.69(s,2H),7.53(s,2H),7.28(t,J＝5.5Hz,2H),2.89-2.81(m,4H),2.02–1.90(m,4H),1.71(dd,J＝15.3,7.6Hz,5H),0.94(ddt,J＝12.5,11.5,7.1Hz,25H),0.72(t,J＝6.7Hz,7H),0.64(td,J＝7.4,1.4Hz,8H)。M/Z＝886.4876。The characterization data for this product D is as follows: 1 H NMR (400 MHz, CDCl 3 ) δ = 7.69 (s, 2H), 7.53 (s, 2H), 7.28 (t, J = 5.5 Hz, 2H), 2.89 - 2.81 (m) , 4H), 2.02–1.90 (m, 4H), 1.71 (dd, J = 15.3, 7.6 Hz, 5H), 0.94 (ddt, J = 12.5, 11.5, 7.1 Hz, 25H), 0.72 (t, J = 6.7 Hz, 7H), 0.64 (td, J = 7.4, 1.4 Hz, 8H). M/Z = 886.4876.
实施例3参阅图3，该有机小分子半导体材料的合成制备工艺可以为：原料E(200mg,274μmol),原料A(222mg,685μmol)加入100ml单口圆底烧瓶瓶，四(三苯基膦)钯(17mg,14.7μmol)在氮气保护下加入反应器，经过充分脱气的二甲基甲酰胺(DMF)(23ml)加入反应器，60摄氏度搅拌约6小时，反应结束后经过水洗，分液，合并有机相。有机相经过无水硫酸钠干燥，旋蒸除去有机溶液，薄板层析技术提纯，得到最终产品D(169mg),收率70％。Embodiment 3 Referring to FIG. 3, the synthetic preparation process of the organic small molecule semiconductor material may be: starting material E (200 mg, 274 μmol), raw material A (222 mg, 685 μmol) added to a 100 ml single-neck round bottom flask, tetrakis(triphenylphosphine) Palladium (17 mg, 14.7 μmol) was added to the reactor under nitrogen, and the fully degassed dimethylformamide (DMF) (23 ml) was added to the reactor and stirred at 60 ° C for about 6 hours. After the reaction, it was washed with water and separated. , combining organic phases. The organic phase was dried over anhydrous sodium sulfate, and then evaporated and evaporated, and then evaporated.
该产品D的表征数据如下：1H NMR(400MHz,CDCl3)δ＝7.69(s,2H),7.53(s,2H),7.28(t,J＝5.5Hz,2H),2.89–2.81(m,4H),2.02–1.90(m,4H),1.71(dd,J＝15.3,7.6Hz,5H),0.94(ddt,J＝12.5,11.5,7.1Hz,25H),0.72(t,J＝6.7Hz, 7H),0.64(td,J＝7.4,1.4Hz,8H)。M/Z＝886.4876。The characterization data for this product D is as follows: 1 H NMR (400 MHz, CDCl 3 ) δ = 7.69 (s, 2H), 7.53 (s, 2H), 7.28 (t, J = 5.5 Hz, 2H), 2.89 - 2.81 (m) , 4H), 2.02–1.90 (m, 4H), 1.71 (dd, J = 15.3, 7.6 Hz, 5H), 0.94 (ddt, J = 12.5, 11.5, 7.1 Hz, 25H), 0.72 (t, J = 6.7 Hz, 7H), 0.64 (td, J = 7.4, 1.4 Hz, 8H). M/Z = 886.4876.
实施例4本发明有机小分子半导体材料的电化学性能可以循环伏安法等测试。以小分子半导体材料F为例，可以将其溶解在无水二氯甲烷中，施加偏压(‐1.8伏‐1.8伏)，得出循环伏安曲线。测试完毕后，在F的无水二氯甲烷溶液中加入少量二茂铁，测试出二茂铁的循环伏安曲线。从而得到小分子半导体材料相对于二茂铁的氧化还原电位(请参阅图7a)。小分子半导体材料的最高分子占据轨道能级(HOMO)和最低分子空轨道能级(LUMO)可通过如下公式计算：Example 4 The electrochemical properties of the organic small molecule semiconductor material of the present invention can be tested by cyclic voltammetry or the like. Taking the small molecular semiconductor material F as an example, it can be dissolved in anhydrous dichloromethane, and a bias voltage (-1.8 volt - 1.8 volt) is applied to obtain a cyclic voltammetry curve. After the test, a small amount of ferrocene was added to the anhydrous dichloromethane solution of F to test the cyclic voltammetry curve of ferrocene. Thereby, the redox potential of the small molecule semiconductor material relative to ferrocene is obtained (see Fig. 7a). The highest molecular occupied orbital level (HOMO) and the lowest molecular empty orbital level (LUMO) of a small molecule semiconductor material can be calculated by the following formula:
EHOMO＝-(Eox onset+5.10)(eV)E HOMO =-(E ox onset +5.10)(eV)
ELUMO＝-(Ered onset+5.10)(eV)E LUMO =-(E red onset +5.10)(eV)
其中，Eox onset是起始氧化电位，Ered onset是起始还原电位。Where E ox onset is the initial oxidation potential and E red onset is the initial reduction potential.
请参阅图6所示系本发明中典型有机小分子半导体材料D、F、G及聚(3-己基噻吩)(P3HT)、二噻吩并苯-噻并[3,4-b]噻吩的共聚物(PTB7)、聚[2,6-(4,4-双-(2-乙基己基)-4H-环戊[2,1-b；3,4-b’]双噻吩)-交替4,7-(2,1,3-苯并噻二唑)](PCPDTBT)的能级。Please refer to FIG. 6 for the copolymerization of typical organic small molecule semiconductor materials D, F, G and poly(3-hexylthiophene) (P3HT) and dithienobenzene-thiato[3,4-b]thiophene in the present invention. (PTB7), poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']bisthiophene)-alternating 4 , the energy level of 7-(2,1,3-benzothiadiazole)] (PCPDTBT).
另及，本发明中典型有机小分子半导体材料D、F、G的电化学性能还可参阅图7b。In addition, the electrochemical properties of typical organic small molecule semiconductor materials D, F, G in the present invention can also be seen in Figure 7b.
实施例5一种典型有机小分子-共轭聚合物复合物的制备工艺可以为：聚(3‐己基噻吩)(P3HT)和小分子半导体材料F各5毫克，加入1毫升氯苯，在50摄氏度下搅拌10小时溶解。Example 5 A typical organic small molecule-conjugated polymer composite can be prepared by: poly(3-hexylthiophene) (P3HT) and small molecular semiconductor material F 5 mg each, adding 1 ml of chlorobenzene at 50 Stir at 90 ° C for 10 hours.
实施例6利用旋涂方法制备复合物薄膜：将实施例5中的复合物溶液在600转/秒的转速下旋转1分钟制备薄膜，膜厚80纳米左右。Example 6 Preparation of a composite film by a spin coating method: A film of the composite solution of Example 5 was rotated at 600 rpm for 1 minute to prepare a film having a film thickness of about 80 nm.
实施例7请参阅图8所示是利用本发明的一种有机小分子半导体材料构建的有机光伏器件，其可设置在一基底上，包括氧化铟锡层(ITO)、空穴传输层、有机光敏层、电子传输层和接触电极，其中各层的材料依次可为ITO、PEDOT:PSS、P3HT:F、PFN、Al，其中PEDOT:PSS为聚(3，4‐乙撑二氧噻吩)和聚苯乙烯磺酸盐的混合物，P3HT为聚(3‐己基噻吩)、F为本发明中典型有 机小分子半导体材料F(图4a)、PFN为聚[9,9‐二辛基芴‐9,9‐双(N,N‐二甲基胺丙基)芴]。再请参阅图9所示是该有机电子器件的I-V测试图谱。Embodiment 7 Please refer to FIG. 8 is an organic photovoltaic device constructed by using an organic small molecule semiconductor material of the present invention, which may be disposed on a substrate, including an indium tin oxide layer (ITO), a hole transport layer, and an organic a photosensitive layer, an electron transport layer and a contact electrode, wherein the materials of each layer may be ITO, PEDOT: PSS, P3HT: F, PFN, Al, wherein PEDOT: PSS is poly(3,4-ethylenedioxythiophene) and a mixture of polystyrene sulfonates, P3HT is poly(3-hexylthiophene), F is typical in the present invention. The small molecule semiconductor material F (Fig. 4a) and PFN are poly[9,9-dioctylindole-9,9-bis(N,N-dimethylaminopropyl) fluorene]. Referring again to Figure 9, the I-V test pattern of the organic electronic device is shown.
综上所述，本发明的有机小分子半导体材料具有小的光谱带隙，长的光谱吸收波长，较低的最高占据轨道及最低空轨道能级，可作为光电材料，尤其是有机光伏中的受体材料，且其还具有制备工艺简单，成本低廉等优点。In summary, the organic small molecule semiconductor material of the invention has a small spectral band gap, a long spectral absorption wavelength, a lower highest occupied orbit and a lowest empty orbital level, and can be used as a photovoltaic material, especially in organic photovoltaics. Receptor material, and it also has the advantages of simple preparation process, low cost and the like.
需要说明的是，在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。It is to be understood that the term "comprises", "comprising" or any other variations thereof is intended to encompass a non-exclusive inclusion, such that a process, method, article, or device that comprises a It also includes other elements that are not explicitly listed, or elements that are inherent to such a process, method, item, or device.
以上所述仅是本发明的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。 The above is only a specific embodiment of the present invention, and it should be noted that those skilled in the art can also make several improvements and retouchings without departing from the principles of the present invention. It should be considered as the scope of protection of the present invention.

Claims (11)

  1. 一种有机小分子半导体材料，其特征在于，包含二芳环并环戊二烯类π共轭单元及芳香基团，并具有如下结构式：An organic small molecule semiconductor material comprising a diarylcyclopentadiene π-conjugated unit and an aromatic group, and having the following structural formula:
    Figure PCTCN2015082416-appb-100001
    Figure PCTCN2015082416-appb-100001
    其中X1、X2独立地选自O、S或Se，X3选自O、S、Se、NR2、C(R2)2或Si(R2)2，R2选自含C数为1-20的直链或支链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，R1选自氢原子、含C数为1-20的直链或支链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，A为吸电子单元。Wherein X 1 , X 2 are independently selected from O, S or Se, X 3 is selected from O, S, Se, NR 2 , C(R 2 ) 2 or Si(R 2 ) 2 , and R 2 is selected from C-containing numbers a linear or branched alkyl group of 1-20, a linear or branched modified alkylaryl or heterocyclic aryl group having a C number of 7-20, and R1 is selected from a hydrogen atom and has a C number of 1-20. A linear or branched alkyl group, a linear or branched modified alkylaryl or heterocyclic aryl group having a C number of 7 to 20, and A is an electron withdrawing unit.
  2. 根据权利要求1所述的有机小分子半导体材料，其特征在于，X1为S，和/或，X3为Si(R2)2。The organic small molecule semiconductor material according to claim 1, wherein X 1 is S, and/or X 3 is Si(R 2 ) 2 .
  3. 根据权利要求1所述的有机小分子半导体材料，其特征在于，所述吸电子单元至少具有下列结构式中的任一种：The organic small molecule semiconductor material according to claim 1, wherein the electron withdrawing unit has at least one of the following structural formulas:
    Figure PCTCN2015082416-appb-100002
    Figure PCTCN2015082416-appb-100002
    其中，R3选自H、含C数为1-20的直链或支链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基。Wherein R 3 is selected from the group consisting of H, a linear or branched alkyl group having a C number of 1 to 20, and a linear or branched modified alkaryl or heterocyclic aryl group having a C number of 7 to 20.
  4. 根据权利要求3所述的有机小分子半导体材料，其特征在于，所述吸电子单元具有下列结构式中的任一种： The organic small molecule semiconductor material according to claim 3, wherein the electron withdrawing unit has any one of the following structural formulas:
    Figure PCTCN2015082416-appb-100003
    Figure PCTCN2015082416-appb-100003
  5. 一种有机小分子半导体材料的合成方法，其特征在于，包括：提供包含二芳环并环戊二烯类π共轭单元的第一化合物与包含芳香基团的第二化合物，经过渡金属催化缩合反应，获得所述有机小分子半导体材料；A method for synthesizing an organic small molecule semiconductor material, comprising: providing a first compound comprising a diarylcyclo and cyclopentadienyl π-conjugated unit and a second compound comprising an aromatic group, catalyzed by a transition metal a condensation reaction to obtain the organic small molecule semiconductor material;
    所述第一化合物具有如下结构式：The first compound has the following structural formula:
    Figure PCTCN2015082416-appb-100004
    Figure PCTCN2015082416-appb-100004
    所述第二化合物具有如下结构式：The second compound has the following structural formula:
    Figure PCTCN2015082416-appb-100005
    Figure PCTCN2015082416-appb-100005
    所述有机小分子半导体材料具有如下结构式：The organic small molecule semiconductor material has the following structural formula:
    Figure PCTCN2015082416-appb-100006
    Figure PCTCN2015082416-appb-100006
    其中，X1、X2独立地选自O、S或Se，X3选自O、S、Se、NR2、C(R2)2或Si(R2)2，X4、X5独立地选自卤素原子、Sn(R4)3、BO(R5)2或包含-O-B-O-的5-7元环状取代或未取代的硼酯，且X4、X5之中有且只有一个为卤素原子，R1选自含C数为1-20的直链或支链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，R4选自含C数为1-4的直链或支链烷基，R5选自氢原子、C数为1-4的直链或支链烷基，A为吸电子单元。Wherein X 1 and X 2 are independently selected from O, S or Se, and X 3 is selected from O, S, Se, NR 2 , C(R 2 ) 2 or Si(R 2 ) 2 , and X 4 and X 5 are independently selected. Is selected from a halogen atom, Sn(R 4 ) 3 , BO(R 5 ) 2 or a 5-7 membered cyclic substituted or unsubstituted boron ester containing -OBO-, and among X 4 and X 5 One is a halogen atom, and R 1 is selected from a linear or branched alkyl group having a C number of 1 to 20, a linear or branched alkylaryl group or a heterocyclic aryl group having a C number of 7 to 20, R 4 is selected from a linear or branched alkyl group having a C number of from 1 to 4, R 5 is selected from a hydrogen atom, a linear or branched alkyl group having a C number of from 1 to 4, and A is an electron withdrawing unit.
  6. 根据权利要求5所述的有机小分子半导体材料的合成方法，其特征在于，所述过渡金属催化缩合反应包括金属催化Suzuki缩合或金属催化Stille缩合反应。The method for synthesizing an organic small molecule semiconductor material according to claim 5, wherein the transition metal catalyzed condensation reaction comprises a metal catalyzed Suzuki condensation or a metal catalyzed Stille condensation reaction.
  7. 一种有机小分子半导体-共轭聚合物复合物，其特征在于，由权利要求 1-7中任一项所述的有机小分子半导体材料与共轭聚合物复合形成，Organic small molecule semiconductor-conjugated polymer composite characterized by the claims The organic small molecule semiconductor material according to any one of 1 to 7, which is formed by complexing with a conjugated polymer,
    所述有机小分子半导体材料包含二芳环并环戊二烯类π共轭单元及芳香基团，并具有如下结构式：The organic small molecule semiconductor material comprises a diarylcyclopentadiene π-conjugated unit and an aromatic group, and has the following structural formula:
    Figure PCTCN2015082416-appb-100007
    Figure PCTCN2015082416-appb-100007
    其中X1、X2独立地选自O、S或Se，X3选自O、S、Se、NR2、C(R2)2或Si(R2)2，R2选自含C数为1-20的直链或支链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，R1选自氢原子、含C数为1-20的直链或支链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基，A为吸电子单元；Wherein X 1 , X 2 are independently selected from O, S or Se, X 3 is selected from O, S, Se, NR 2 , C(R 2 ) 2 or Si(R 2 ) 2 , and R 2 is selected from C-containing numbers a linear or branched alkyl group of 1-20, a linear or branched modified alkylaryl or heterocyclic aryl group having a C number of 7-20, and R1 is selected from a hydrogen atom and has a C number of 1-20. a linear or branched alkyl group, a linear or branched modified alkylaryl or heterocyclic aryl group having a C number of 7 to 20, and A is an electron withdrawing unit;
    其中，所述共轭聚合物的最高分子占据轨道能级较所述有机小分子半导体材料的最高分子占据轨道能级高至少0.2eV，所述共轭聚合物的最低分子空轨道能级较所述有机小分子半导体材料的最低分子空轨道能级高至少0.2eV。Wherein the highest molecular occupied orbital energy level of the conjugated polymer is at least 0.2 eV higher than the highest molecular occupied orbital energy level of the organic small molecular semiconductor material, and the lowest molecular empty orbital energy level of the conjugated polymer is higher than The lowest molecular orbital energy level of the organic small molecule semiconductor material is at least 0.2 eV.
  8. 根据权利要求7所述的有机小分子半导体-共轭聚合物复合物，其特征在于所述共轭聚合物至少选自聚(3-己基噻吩)、二噻吩并苯-噻并[3,4-b]噻吩的共聚物、聚[2,6-(4,4-双-(2-乙基己基)-4H-环戊[2,1-b；3,4-b’]双噻吩)-交替4,7-(2,1,3-苯并噻二唑)]中的任一种。The organic small molecule semiconductor-conjugated polymer composite according to claim 7, wherein the conjugated polymer is at least selected from the group consisting of poly(3-hexylthiophene) and dithienobenzene-thiazino[3,4 -b] copolymer of thiophene, poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']bisthiophene) - Alternate any of 4,7-(2,1,3-benzothiadiazole).
  9. 根据权利要求7所述的有机小分子半导体-共轭聚合物复合物，其特征在于，X1为S，和/或，X3为Si(R2)2。The organic small molecule semiconductor-conjugated polymer composite according to claim 7, wherein X 1 is S, and/or X 3 is Si(R 2 ) 2 .
  10. 根据权利要求7所述的有机小分子半导体-共轭聚合物复合物，其特征在于，所述吸电子单元至少具有下列结构式中的任一种： The organic small molecule semiconductor-conjugated polymer composite according to claim 7, wherein the electron withdrawing unit has at least one of the following structural formulas:
    Figure PCTCN2015082416-appb-100008
    Figure PCTCN2015082416-appb-100008
    其中，R3选自H、含C数为1-20的直链或支链烷基、含C数为7-20的直链或支链修饰的烷芳基或杂环芳基。Wherein R 3 is selected from the group consisting of H, a linear or branched alkyl group having a C number of 1 to 20, and a linear or branched modified alkaryl or heterocyclic aryl group having a C number of 7 to 20.
  11. 根据权利要求10所述的有机小分子半导体-共轭聚合物复合物，其特征在于，所述吸电子单元具有下列结构式中的任一种：The organic small molecule semiconductor-conjugated polymer composite according to claim 10, wherein the electron withdrawing unit has any one of the following structural formulas:
    Figure PCTCN2015082416-appb-100009
    Figure PCTCN2015082416-appb-100009
PCT/CN2015/082416 2014-08-01 2015-06-26 Organic small molecular semiconductor material, and synthetic method and use thereof WO2016015533A1 (en)

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