CN103360322A - Organic semiconductor material made of benzimidazole substituted pyrene as well as preparation method and applications thereof - Google Patents

Organic semiconductor material made of benzimidazole substituted pyrene as well as preparation method and applications thereof Download PDF

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CN103360322A
CN103360322A CN2012100895065A CN201210089506A CN103360322A CN 103360322 A CN103360322 A CN 103360322A CN 2012100895065 A CN2012100895065 A CN 2012100895065A CN 201210089506 A CN201210089506 A CN 201210089506A CN 103360322 A CN103360322 A CN 103360322A
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benzoglyoxaline
pyrene
organic semiconductor
semiconductor material
compd
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周明杰
王平
梁禄生
陈吉星
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention relates to the technical field of organic semiconductor materials, and provides an organic semiconductor material made of benzimidazole substituted pyrene. The molecular structure general formula of the material is as shown in the specification, wherein, A1, A2, A3 and A4 in the formula are respectively selected from any one of H and a group as shown in the specification, and at least one of A1, A2, A3 and A4 is a group as shown in the specification. The invention also provides a preparation method and applications of the organic semiconductor material made of benzimidazole substituted pyrene. The benzimidazole substituted pyrene material has a favorable electronic transmission performance and high light-emitting efficiency, and has an application prospect in the photoelectric field.

Description

Benzoglyoxaline replaces organic semiconductor material of pyrene and its preparation method and application
Technical field
The invention belongs to the organic semiconductor material technical field, be specifically related to a kind of benzoglyoxaline and replace organic semiconductor material of pyrene and its preparation method and application.
Background technology
Along with the development of information age, have efficient, energy-conservation, the organic EL display (OLEDs) of lightweight and the concern that the big area white-light illuminating more and more is subject to people.The OLED technology is paid close attention to by the scientist in the whole world, and relevant enterprise and laboratory are all in the research and development of carrying out this technology.As a kind of novel LED technology, have active illuminating, light, thin, good contrast, energy consumption organic electroluminescence device low, that can be made into the characteristics such as flexible device material has been proposed higher requirement.But the mobility in hole is often very high in the organic semiconductor material, is the majority carrier in the organic electroluminescence device, so electronics has just become relative minority carrier.Yet according to luminescence process and the mechanism of organic electroluminescent, the charge balance between current carrier has unusual meaning to the raising of the performances such as efficient of device.
1987, the Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in the organic electroluminescent research.Because the blue light energy is the highest, material just can obtain green glow and ruddiness by several different methods as long as have preferably.So if realize the application purposes such as panchromatic demonstration and illumination, blue light material is even more important in the three primary colours.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective of prior art, and organic semiconductor material of a kind of benzoglyoxaline replacement pyrene and its preparation method and application is provided.
The embodiment of the invention is achieved in that first aspect provides a kind of benzoglyoxaline to replace the organic semiconductor material of pyrene, and general formula of molecular structure is as follows:
Figure BDA0000148740720000021
In the formula, A 1, A 2, A 3And A 4Be selected from respectively H and
Figure BDA0000148740720000022
In any one, and A 1, A 2, A 3And A 4In at least one is
Figure BDA0000148740720000023
Another purpose of the embodiment of the invention is to provide above-mentioned benzoglyoxaline to replace the preparation method of the organic semiconductor material of pyrene, and described preparation method comprises the steps:
Choose compd A and compd B, the chemical structural formula of compd A is as follows,
Figure BDA0000148740720000024
The chemical structural formula of compd B is as follows,
Figure BDA0000148740720000025
Under inert gas environment, under the condition that organo-metallic catalyst system, basic solution and organic solvent exist, compd A and compd B are carried out the Suzuki reaction, obtain the organic semiconductor material that benzoglyoxaline replaces pyrene, the structural formula of this material is as follows:
Figure BDA0000148740720000031
In the formula, A 1, A 2, A 3And A 4Be selected from respectively H and
Figure BDA0000148740720000032
In any one, and A 1, A 2, A 3And A 4In at least one is
Figure BDA0000148740720000033
And above-mentioned benzoglyoxaline replaces the application of organic semiconductor material in organic electroluminescence device of pyrene, and wherein, the organic semiconductor material that benzoglyoxaline replaces pyrene is luminescent layer.
Above-mentioned benzoglyoxaline replaces the application of organic semiconductor material in solar device of pyrene, and wherein, the organic semiconductor material that described benzoglyoxaline replaces pyrene is active coating.
The benzoglyoxaline of the embodiment of the invention replaces the organic semiconductor material of pyrene, the fused ring compound that pyrene is comprised of four benzene, has preferably rigid structure, benzoglyoxaline is the electron deficiency group, can improve the electronic transmission performance of material, itself also be the rigid structure on a plane simultaneously, can improve equally the thermostability of material, by having rigid structure, highly symmetrical pyrene as structural motif and benzoglyoxaline building-up reactions, carry out chemically modified, construct novel organic conjugate functional compounds.This material has preferably carrier transmission performance and high thermostability.This material preparation process is simple, is easy to operate and control, and production cost is low, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is preparation method's schema that the benzoglyoxaline of the embodiment of the invention replaces the organic semiconductor material of pyrene;
Fig. 2 replaces the organic semiconductor material of pyrene as the structural representation of the organic electroluminescence device of making luminescent layer with the benzoglyoxaline of the embodiment of the invention;
Fig. 3 replaces the organic semiconductor material of pyrene as the structural representation of the polymer solar cell device of active coating with the benzoglyoxaline of the embodiment of the invention;
Fig. 4 replaces the organic semiconductor material of pyrene as the structural representation of the organic field effect tube device of organic semiconductor layer with the benzoglyoxaline of the embodiment of the invention;
Fig. 5 is the electroluminescent spectrum figure that the benzoglyoxaline of the embodiment of the invention replaces the organic semiconductor material of pyrene.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
See also Fig. 1, the benzoglyoxaline that is depicted as the embodiment of the invention replaces the general formula of molecular structure of the organic semiconductor material of pyrene:
Figure BDA0000148740720000041
In the formula, A 1, A 2, A 3And A 4Be selected from respectively H and
Figure BDA0000148740720000042
In any one, and A 1, A 2, A 3And A 4In at least one is
Preferably, A 1, A 2, A 3And A 4Be all Because the introducing of benzoglyoxaline so that the electronic mobility of material improves, is conducive to the balance of electric charge.
Replace in the organic semiconductor material of pyrene at above-mentioned benzoglyoxaline, pyrene is a highly symmetrical condensed-nuclei aromatics, is a two dimensional structure with larger rigidity.Pyrene is carried out suitable chemically modified, and construct novel organic conjugate functional materials as structural motif, produce unique optics and photoelectronics behavior.The mobility in hole is often very high in the organic semiconductor material, and it is the majority carrier in the organic electroluminescence device, and therefore, electronics just becomes relatively few current carrier.But according to the luminescence process and mechanism of organic electroluminescent, the charge balance between current carrier has unusual meaning to the raising of the performances such as efficient of device.And benzoglyoxaline is the electron deficiency group, and its introducing can improve electronic mobility, is conducive to charge balance, obtains higher luminous efficiency.
See also Fig. 1, the preparation method that above-mentioned benzoglyoxaline replaces the organic semiconductor material of pyrene comprises the steps:
S01: choose compd A and compd B
The chemical structural formula of compd A is as follows,
Figure BDA0000148740720000052
The chemical structural formula of compd B is as follows,
S02: under inert gas environment, under the condition that organo-metallic catalyst system, basic solution and organic solvent exist, compd A and compd B are carried out the Suzuki reaction, obtain the organic semiconductor material that benzoglyoxaline replaces pyrene, the structural formula of this material is as follows:
Figure BDA0000148740720000061
In the formula, A 1, A 2, A 3And A 4Be selected from respectively H and In any one, and A 1, A 2, A 3And A 4In at least one is
Figure BDA0000148740720000063
In step S01, compd A and compd B can directly be buied from the market or prepare by existing synthetic method.
In step S02, organo-metallic catalyst is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride or three (dibenzalacetones), two palladiums, wherein, the organo-metallic catalyst addition is 0.001～0.1 times of mole dosage of compd A;
The temperature of Suzuki coupling reaction is 70 ℃～120 ℃, and the time is 20～48h;
The mole dosage of described compd A is 1: 1～1: 8 with the mole dosage of compd B ratio;
Organic solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene and the toluene;
Basic solution comprises Cs 2CO 3, K 2CO 3, Na 2CO 3Or Li 2CO 3A kind of in the solution, the consumption of basic solution is 20～25 times of mole dosage of compd A;
The organic semiconductor material that the benzoglyoxaline of present embodiment replaces pyrene can be applicable to organic photoelectrical material, organic electroluminescence device, organic solar batteries device, organic field effect tube, the medium field of organic light storage device and/or organic laser apparatus.For example, above-mentioned benzoglyoxaline replaces the organic semiconductor material of pyrene, during as organic electroluminescence device, can be used as luminescent layer.All the other organic light storage devices, organic non-linear optical properties and organic laser apparatus and following similar all are to replace the organic semiconductor material of pyrene as its optical memory material, nonlinear material, laserable material or semiconductor material etc. with the benzoglyoxaline of present embodiment.
Embodiment one:
The organic semiconductor material 2-phenyl-1-(4-(pyrene-1-yl) phenyl) of the benzoglyoxaline replacement pyrene of present embodiment-1H-benzoglyoxaline (PPBi), its structural formula is as follows:
Figure BDA0000148740720000071
Above-mentioned PPBi material preparation step is as follows:
The preparation of 2-phenyl-1-(4-(pyrene-1-yl) phenyl)-1H-benzoglyoxaline (PPBi):
Figure BDA0000148740720000072
Compd A and compd B can directly be buied from the market.
With 1-bromine pyrene 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid 3.3mmol; 0.09mmol tetra-triphenylphosphine palladium join in the reactor; vacuumize, after the logical nitrogen circulation 3 times; reaction system is under the nitrogen protection, and adding 55mL anhydrous tetrahydrofuran solution, 30ml concentration are the Na of 2mol/L 2CO 3The aqueous solution is adjusted to 75 ℃ with temperature of reaction system, back flow reaction 20h.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, obtain crude product after revolving the steaming desolventizing, obtain solid product 2-phenyl-1-(4-(pyrene-1-yl) phenyl)-1H-benzoglyoxaline through the silica gel column chromatography separating-purifying.Productive rate: 92%.MS：m/z?471(M +)。
Detect by the organic semiconductor material that contains naphthalene of thermogravimetric analyzer (TGA) to the embodiment of the invention, analysis condition is nitrogen atmosphere, and when sweep velocity was 10 ℃/min, organic semiconductor material 5% heat decomposition temperature was 392 ℃ among the embodiment of acquisition.
Embodiment two:
(4-(6-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyrene-1-yl) phenyl)-its structural formula of 1H-benzoglyoxaline (DPPBi) is as follows for the organic semiconductor material 2-phenyl-1-of the benzoglyoxaline replacement pyrene of present embodiment:
Figure BDA0000148740720000081
Above-mentioned DPPBi material preparation step is as follows:
The preparation of 2-phenyl-1-(4-(6-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyrene-1-yl) phenyl)-1H-benzoglyoxaline (DPPBi):
Figure BDA0000148740720000082
With 1; 6-dibromo pyrene 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid 6.6mmol; tetra-triphenylphosphine palladium 0.27mmol joins in the reaction flask; vacuumize, after the logical nitrogen circulation 3 times; make reaction system be in anaerobic state, under the nitrogen protection, add the K of anhydrous tetrahydrofuran solution 55mL, 2mol/L 2CO 3Aqueous solution 35ml is heated to 70 ℃ of back flow reaction 40h with mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase is washed with sodium chloride aqueous solution, and drying is revolved and is obtained crude product after steaming desolventizing, obtains solid product through the silica gel column chromatography separating-purifying.Productive rate: 90%.MS：m/z?740(M +)。
Detect by the organic semiconductor material that contains naphthalene of thermogravimetric analyzer (TGA) to the embodiment of the invention, analysis condition is nitrogen atmosphere, and when sweep velocity was 10 ℃/min, organic semiconductor material 5% heat decomposition temperature was 400 ℃ among the embodiment of acquisition.
Embodiment three:
(4-(3 for the organic semiconductor material 1-of the benzoglyoxaline replacement pyrene of present embodiment, 6,8-three (4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyrene-1-yl) phenyl)-and 2-phenyl-1H-benzoglyoxaline (TPPBi), its structural formula is as follows:
Figure BDA0000148740720000091
Above-mentioned TPPBi material preparation step is as follows:
The preparation of 1-(4-(3,6,8-three (4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyrene-1-yl) phenyl)-2-phenyl-1H-benzoglyoxaline (TPPBi):
With 1; 3; 6; 8-tetrabromo pyrene 3mmol, [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid 14mmol, tetra-triphenylphosphine palladium 0.3mmol joins in the reaction flask; vacuumize, after the logical nitrogen circulation 3 times; make reaction system be in anaerobic state, under the nitrogen protection, add the Cs of anhydrous tetrahydrofuran solution 60mL, 2mol/L 2CO 3Aqueous solution 34ml is heated to 85 ℃ of back flow reaction 48h with mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase is washed with sodium chloride aqueous solution, and drying is revolved and is obtained crude product after steaming desolventizing, through the silica gel column chromatography separating-purifying, obtains solid product.Productive rate: 66%.MS：m/z?1276(M +)。
Detect by the organic semiconductor material that contains naphthalene of thermogravimetric analyzer (TGA) to the embodiment of the invention, analysis condition is nitrogen atmosphere, and when sweep velocity was 10 ℃/min, organic semiconductor material 5% heat decomposition temperature was 410 ℃ among the embodiment of acquisition.
Embodiment four: the organic semiconductor material 2-phenyl-1-(4-(pyrene-1-yl) phenyl) of the benzoglyoxaline replacement pyrene of present embodiment-1H-benzoglyoxaline (PPBi), and with reference to embodiment one,
With 1-bromine pyrene 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid 24mmol; 0.024mmol tetra-triphenylphosphine palladium join in the reactor; vacuumize, after the logical nitrogen circulation 3 times; reaction system is under the nitrogen protection, and adding 55mL glycol dimethyl ether, 300ml concentration are the Li of 2mol/L 2CO 3The aqueous solution is adjusted to 95 ℃ with temperature of reaction system, back flow reaction 20h.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, obtain crude product after revolving the steaming desolventizing, obtain solid product 2-phenyl-1-(4-(pyrene-1-yl) phenyl)-1H-benzoglyoxaline through the silica gel column chromatography separating-purifying.Productive rate: 72%.MS：m/z417(M +)。
Detect by the organic semiconductor material that contains naphthalene of thermogravimetric analyzer (TGA) to the embodiment of the invention, analysis condition is nitrogen atmosphere, and when sweep velocity was 10 ℃/min, organic semiconductor material 5% heat decomposition temperature was 392 ℃ among the embodiment of acquisition.
Embodiment five: the organic semiconductor material 2-phenyl-1-(4-(pyrene-1-yl) phenyl) of the benzoglyoxaline replacement pyrene of present embodiment-1H-benzoglyoxaline (PPBi), and with reference to embodiment one,
With 1-bromine pyrene 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid 15mmol; 0.3mmol three (dibenzalacetone) two palladium 0.4mmol join in the reactor; vacuumize, after the logical nitrogen circulation 3 times; reaction system is under the nitrogen protection, and adding 55mL anhydrous tetrahydrofuran solution, 150ml concentration are the Li of 2mol/L 2CO 3The aqueous solution is adjusted to 75 ℃ with temperature of reaction system, back flow reaction 20h.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, obtain crude product after revolving the steaming desolventizing, obtain solid product 2-phenyl-1-(4-(pyrene-1-yl) phenyl)-1H-benzoglyoxaline through the silica gel column chromatography separating-purifying.Productive rate: 86%.MS：m/z417(M +)。
Detect by the organic semiconductor material that contains naphthalene of thermogravimetric analyzer (TGA) to the embodiment of the invention, analysis condition is nitrogen atmosphere, and when sweep velocity was 10 ℃/min, organic semiconductor material 5% heat decomposition temperature was 392 ℃ among the embodiment of acquisition.
Embodiment six: the organic semiconductor material 2-phenyl-1-(4-(6-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyrene-1-yl) phenyl) of the benzoglyoxaline replacement pyrene of present embodiment-1H-benzoglyoxaline (DPPBi), with reference to embodiment two
With 1; 6-dibromo pyrene 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid 6.6mmol; two (triphenylphosphine) palladium chloride 0.003mmol joins in the reaction flask; vacuumize, after the logical nitrogen circulation 3 times; make reaction system be in anaerobic state, under the nitrogen protection, add the K of toluene 55mL, 2mol/L 2CO 3Aqueous solution 35ml is heated to 120 ℃ of back flow reaction 48h with mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase is washed with sodium chloride aqueous solution, and drying is revolved and is obtained crude product after steaming desolventizing, obtains solid product through the silica gel column chromatography separating-purifying.Productive rate: 85%.MS：m/z?740(M +)。
Detect by the organic semiconductor material that contains naphthalene of thermogravimetric analyzer (TGA) to the embodiment of the invention, analysis condition is nitrogen atmosphere, and when sweep velocity was 10 ℃/min, organic semiconductor material 5% heat decomposition temperature was 400 ℃ among the embodiment of acquisition.
Embodiment seven: the organic semiconductor material 2-phenyl-1-(4-(6-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyrene-1-yl) phenyl) of the benzoglyoxaline replacement pyrene of present embodiment-1H-benzoglyoxaline (DPPBi), with reference to embodiment two
With 1,6-dibromo pyrene 3mmol, (4-(4 for 2-phenyl-1-; 4; 5,5-tetramethyl--1,3; 2-dioxa boron-2-yl) phenyl)-1H-benzoglyoxaline 6.2mmol; three (dibenzalacetone) two palladium 0.027mmol join in the reaction flask, vacuumize, after the logical nitrogen circulation 3 times, make reaction system be in anaerobic state; under the nitrogen protection, add the Cs of toluene 50mL, 2mol/L 2CO 3Aqueous solution 35ml is heated to 120 ℃ of back flow reaction 48h with mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase is washed with sodium chloride aqueous solution, and drying is revolved and is obtained crude product after steaming desolventizing, obtains solid product through the silica gel column chromatography separating-purifying.Productive rate: 81%.MS：m/z?740(M +)。
Detect by the organic semiconductor material that contains naphthalene of thermogravimetric analyzer (TGA) to the embodiment of the invention, analysis condition is nitrogen atmosphere, and when sweep velocity was 10 ℃/min, organic semiconductor material 5% heat decomposition temperature was 400 ℃ among the embodiment of acquisition.
See also Fig. 2, show the organic electroluminescence device that adopts the organic semiconductor material of benzoglyoxaline replacement pyrene in above-described embodiment, it comprises glass-base 31, anode 32, hole transmission layer 33, luminescent layer 34, hole blocking layer 35, electron transfer layer 36, buffer layer 37 and the negative electrode 38 that is cascading.Anode 32 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/; Hole transmission layer 33 can be N, N '-two (Alpha-Naphthyl)-N, N '-phenylbenzene-4,4 '-diamines (NPB); Luminescent layer 34 comprises the organic semiconductor material of the benzoglyoxaline replacement pyrene in the embodiment of the invention; Hole blocking layer 35 can be 2,9-dimethyl-4,7-phenylbenzene-9,10-phenanthroline (BCP); Electron transfer layer 36 can be oxine aluminium; Buffer layer 37 can adopt LiF etc., but is not limited to this.Negative electrode 38 can be but be not limited to metal A l or Ba etc.Thereby, in a specific embodiment, luminescent layer 34 is 2-phenyl-1-(4-(6-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyrene-1-yl) phenyl)-1H-benzoglyoxaline (DPPBi), and the organic electroluminescence device representation is: glass/ITO/NPB/DPPBi/BCP/8-hydroxyquinoline aluminum/LiF/Al.Each layer can adopt existing method to form, with the method fabricate devices of vacuum evaporation.Test through at room temperature, under the atmospheric environment, this OLED device has been obtained 3.9% external quantum efficiency.
Fig. 5 show should use-case the luminescent spectrum figure of electroluminescent device when voltage is 7.5V, from Fig. 5 can, its maximum emission wavelength belongs to dark blue optical range at 456nm.
Fig. 3 is that benzoglyoxaline replaces the organic semiconductor material of pyrene as the solar device structural representation of active coating.Solar cell device comprises the glass-base 41 that stacks gradually, transparent anode 42, middle supplementary layer 43, active coating 44, negative electrode 45, middle supplementary layer 43 adopts polyethylene dioxy base thiophene: polystyrene-sulfonic acid matrix material (referred to as PEDOT:PSS), active coating 44 comprises electron donor material and electron acceptor material, (4-(3 for 1-in the electron donor material employing embodiment of the invention three, 6,8-three (4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyrene-1-yl) phenyl)-2-phenyl-1H-benzoglyoxaline (TPPBi), electron acceptor material can be [6,6] phenyl-C 61-methyl-butyrate (referred to as PCBM).Transparent anode 42 can adopt tin indium oxide (referred to as ITO).Negative electrode 45 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc.Wherein, glass-base 41 can be used as bottom, during making, choose ito glass, and after ultrasonic cleaning, use oxygen plasma treatment, supplementary layer 43 in the middle of ito glass applies, again the benzoglyoxaline in the embodiment of the invention is replaced the organic semiconductor material of pyrene and electron acceptor material be coated on after by blend in the middle of on the supplementary layer 43, form active coating 44, and then by vacuum evaporation technology deposition cathode 45 on active coating 44, obtain above-mentioned solar cell device.In a preferred embodiment, the thickness of transparent anode 42, middle supplementary layer 43, active coating 44, double-metal layer Ca and Al layer be respectively 170,40,150,70nm.As shown in Figure 4, under illumination, light transmission glass-base 41 and ITO electrode 42, the benzoglyoxaline in the active coating 44 replaces the organic semiconductor material absorbing light energy of pyrene, and produces exciton, these excitons are moved to electron donor(ED)/acceptor material at the interface again, and with transfer transport to electron acceptor material, such as PCBM, realize the separation of electric charge, thereby form freely current carrier, i.e. freely electronics and hole.These freely electronics along electron acceptor material to metallic cathode transmission and collected by negative electrode, the hole is along electron donor material to ito anode transmission and collected by anode freely, thereby forms photoelectric current and photovoltage, realizes opto-electronic conversion, during external load 46, can power to it.This organic materials can also alleviate the quality of solar cell device, and making method is simple, is convenient to large batch of preparation.
See also Fig. 4, benzoglyoxaline is shown replaces the organic semiconductor material of pyrene as the structural representation of the organic field effect tube of organic semiconductor layer.Organic field effect tube comprises substrate 51, insulation layer 52, decorative layer 53, the organic semiconductor layer 54 that is cascading and is located at source electrode 55 and drain electrode 56 on the organic semiconductor layer 54.Wherein, substrate 51 can be but be not limited to highly doped silicon chip (Si) that insulation layer 52 can be but be not limited to micro-nano (such as 450nm) thick SiO 21-(4-(3,6,8-three (4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyrene-1-yl) phenyl) in the organic semiconductor layer 54 employing embodiment of the invention three-2-phenyl-1H-benzoglyoxaline (TPPBi).Source electrode 55 and drain electrode 56 all can adopt but be not limited to gold.Decorative layer 53 can be but be not limited to octadecyl trichlorosilane alkane (OTS).Substrate 51, insulation layer 52, decorative layer 53 and source electrode 55 and drain electrode 56 all can adopt existing method to form.Organic semiconductor layer 54 can be that (4-(3 for 1-in the embodiment of the invention three, 6,8-three (4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyrene-1-yl) phenyl)-2-phenyl-1H-benzoglyoxaline (TPPBi) is spun on the insulation layer 52 of being modified by decorative layer 53.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a benzoglyoxaline replaces the organic semiconductor material of pyrene, it is characterized in that the general formula of molecular structure of this material is as follows:
Figure FDA0000148740710000011
In the formula, A 1, A 2, A 3And A 4Be selected from respectively H and
Figure FDA0000148740710000012
In any one, and A 1, A 2, A 3And A 4In at least one is
Figure FDA0000148740710000013
2. benzoglyoxaline as claimed in claim 1 replaces the organic semiconductor material of pyrene, it is characterized in that described A 1, A 2, A 3And A 4Be all
3. the preparation method of the organic semiconductor material of a benzoglyoxaline replacement pyrene is characterized in that it comprises the steps:
Choose compd A and compd B, the chemical structural formula of compd A is as follows,
The chemical structural formula of compd B is as follows,
Under inert gas environment, under the condition that organo-metallic catalyst system, basic solution and organic solvent exist, compd A and compd B are carried out the Suzuki reaction, obtain the organic semiconductor material that benzoglyoxaline replaces pyrene, the structural formula of this material is as follows:
Figure FDA0000148740710000022
In the formula, A 1, A 2, A 3And A 4Be selected from respectively H and In any one, and A 1, A 2, A 3And A 4In at least one is
4. benzoglyoxaline as claimed in claim 3 replaces the preparation method of the organic semiconductor material of pyrene, it is characterized in that, described organo-metallic catalyst is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride or three (dibenzalacetones), two palladiums, wherein, the organo-metallic catalyst addition is 0.001～0.1 times of mole dosage of compd A.
5. benzoglyoxaline as claimed in claim 3 replaces the preparation method of the organic semiconductor material of pyrene, it is characterized in that the temperature of described Suzuki coupling reaction is 70 ℃～120 ℃, and the time is 20～48h.
6. benzoglyoxaline as claimed in claim 3 replaces the preparation method of the organic semiconductor material of pyrene, it is characterized in that the mole dosage of described compd A is 1: 1～1: 8 with the mole dosage of compd B ratio.
7. benzoglyoxaline as claimed in claim 3 replaces the preparation method of the organic semiconductor material of pyrene, it is characterized in that, described organic solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene and the toluene.
8. benzoglyoxaline as claimed in claim 3 replaces the preparation method of the organic semiconductor material of pyrene, it is characterized in that described basic solution comprises Cs 2CO 3, K 2CO 3, Na 2CO 3Or Li 2CO 3A kind of in the solution, the consumption of basic solution is 20～25 times of mole dosage of compd A.
9. an organic electroluminescence device comprises luminescent layer, it is characterized in that, described luminescent layer is the organic semiconductor material that replaces pyrene such as each described benzoglyoxaline of claim 1～2.
10. a solar device comprises active coating, it is characterized in that, described active coating is the organic semiconductor material that replaces pyrene such as each described benzoglyoxaline of claim 1～2.
CN2012100895065A 2012-03-30 2012-03-30 Organic semiconductor material made of benzimidazole substituted pyrene as well as preparation method and applications thereof Pending CN103360322A (en)

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Application publication date: 20131023