CN103360368A - Organic semiconductor material containing benzimidazole substituted pyridine as well as preparation method and applications thereof - Google Patents

Organic semiconductor material containing benzimidazole substituted pyridine as well as preparation method and applications thereof Download PDF

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CN103360368A
CN103360368A CN2012100895012A CN201210089501A CN103360368A CN 103360368 A CN103360368 A CN 103360368A CN 2012100895012 A CN2012100895012 A CN 2012100895012A CN 201210089501 A CN201210089501 A CN 201210089501A CN 103360368 A CN103360368 A CN 103360368A
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organic semiconductor
benzoglyoxaline
semiconductor material
substituted pyridines
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 of benzimidazole substituted pyridine. The molecule structure general formula of the material is as shown in the specification. In the formula, Ar is H or a formula as shown in the specification, and Ar is at least one group as shown in the specification. The invention also provides a preparation method and applications of the organic semiconductor material containing benzimidazole substituted pyridine. The material containing benzimidazole substituted pyridine has a favorable electric transmission performance and a stable performance.

Description

Contain organic semiconductor material of benzoglyoxaline substituted pyridines 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 organic semiconductor material that contains the benzoglyoxaline substituted pyridines 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.
Therefore the electron transport material that develops high mobility has very important significance to the lifting of organic electroluminescent performance.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective of prior art, and a kind of organic semiconductor material that contains the benzoglyoxaline substituted pyridines and its preparation method and application is provided.
The embodiment of the invention is achieved in that first aspect provides a kind of organic semiconductor material that contains the benzoglyoxaline substituted pyridines, and general formula of molecular structure is as follows:
Figure BDA0000148736080000021
In the formula, Ar be H or
Figure BDA0000148736080000022
And Ar at least one be
Another purpose of the embodiment of the invention is to provide the above-mentioned preparation method who contains the organic semiconductor material of benzoglyoxaline substituted pyridines, and described preparation method comprises the steps:
Choose compd A and compd B, the chemical structural formula of compd A is as follows,
Figure BDA0000148736080000024
The chemical structural formula of compd B is as follows,
Figure BDA0000148736080000025
Or
Figure BDA0000148736080000026
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 containing the organic semiconductor material of benzoglyoxaline substituted pyridines, the structural formula of this material is as follows:
Figure BDA0000148736080000027
In the formula, Ar be H or
Figure BDA0000148736080000028
And Ar at least one be
Figure BDA0000148736080000029
And, the above-mentioned application of organic semiconductor material in organic electroluminescence device that contains the benzoglyoxaline substituted pyridines, wherein, the organic semiconductor material that contains the benzoglyoxaline substituted pyridines is electron transfer layer.
The above-mentioned application of organic semiconductor material in solar device that contains the benzoglyoxaline substituted pyridines, wherein, the described organic semiconductor material that contains the benzoglyoxaline substituted pyridines is active coating.
The above-mentioned application of organic semiconductor material in organic field effect tube that contains the benzoglyoxaline substituted pyridines, wherein, the described organic semiconductor material that contains the benzoglyoxaline substituted pyridines is organic semiconductor layer.
The organic semiconductor material that contains the benzoglyoxaline substituted pyridines of the embodiment of the invention, pyridine are the aromatic hydrocarbon of the nitrogen heterocyclic ring structure of six-ring, are the electron deficiency groups, can improve the electronic transmission performance of material; Benzoglyoxaline also is the nitrogen-containing benzoheterocycle structure of electron deficiency, can improve equally the electronic transmission performance of material; Can increase the volume steric hindrance of molecular structure at 1,2 upper substituted-phenyl of benzoglyoxaline, can improve the material thermostability, by having benzoglyoxaline substituted pyridines building-up reactions, carry out chemically modified, construct novel organic conjugate functional compounds.This material has preferably electronic transmission performance and thermal stability.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 of the organic semiconductor material that contains the benzoglyoxaline substituted pyridines of the embodiment of the invention;
Fig. 2 is with the organic semiconductor material that contains the benzoglyoxaline substituted pyridines of the embodiment of the invention structural representation as the organic electroluminescence device of electron transfer layer;
Fig. 3 is with the organic semiconductor material that contains the benzoglyoxaline substituted pyridines of the embodiment of the invention structural representation as the polymer solar cell device of active coating;
Fig. 4 is with the organic semiconductor material that contains the benzoglyoxaline substituted pyridines of the embodiment of the invention structural representation as the organic field effect tube device of organic semiconductor layer.
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, be depicted as the general formula of molecular structure of the organic semiconductor material that contains the benzoglyoxaline substituted pyridines of the embodiment of the invention:
Figure BDA0000148736080000041
In the formula, the chemical structural formula of compd B is as follows,
Figure BDA0000148736080000042
Or
Figure BDA0000148736080000043
Wherein, the position of substitution of two Ar is respectively any one replacement in 2,6,2,5,2,4 or 3,5.
In the above-mentioned organic semiconductor material that contains the benzoglyoxaline substituted pyridines, pyridine is the aromatic hydrocarbon of the nitrogen heterocyclic ring structure of six-ring, is the electron deficiency group, can improve the electronic transmission performance of material; Benzoglyoxaline also is the nitrogen-containing benzoheterocycle structure of electron deficiency, can improve equally the electronic transmission performance of material; The volume steric hindrance of molecular structure can be increased at 1,2 upper substituted-phenyl of benzoglyoxaline, the material thermostability can be improved.
See also Fig. 1, the above-mentioned preparation method who contains the organic semiconductor material of benzoglyoxaline substituted pyridines comprises the steps:
S01: choose compd A and compd B
The chemical structural formula of compd A is as follows,
Figure BDA0000148736080000044
The chemical structural formula of compd B is as follows, Or
Figure BDA0000148736080000046
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 containing the organic semiconductor material of benzoglyoxaline substituted pyridines, the structural formula of this material is as follows:
Figure BDA0000148736080000051
In the formula, Ar be H or
Figure BDA0000148736080000052
And Ar at least one be
Figure BDA0000148736080000053
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 compd A is 1: 2～1: 3 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 contains the benzoglyoxaline substituted pyridines of the present embodiment 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, the above-mentioned organic semiconductor material that contains the benzoglyoxaline substituted pyridines during as organic electroluminescence device, can be used as electron transfer layer.All the other organic light storage devices, organic non-linear optical properties and organic laser apparatus and following similar all are with the organic semiconductor material that contains the benzoglyoxaline substituted pyridines of the present embodiment optical memory material, nonlinear material, laserable material or the semiconductor material etc. as it.
Embodiment one:
The organic semiconductor material 2-phenyl-1-that contains the benzoglyoxaline substituted pyridines of the present embodiment (4-(5-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridin-3-yl) phenyl)-1H-benzoglyoxaline (35DPBiPy), its structural formula is as follows:
Figure BDA0000148736080000061
Above-mentioned 35DPBiPy material preparation step is as follows:
The preparation of 2-phenyl-1-(4-(5-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridin-3-yl) phenyl)-1H-benzoglyoxaline (35DPBiPy):
Figure BDA0000148736080000062
Compd A can directly buy from the market or according to document (chemical reagent, 2010,32 (3), 261-262) disclosed method obtains.
Compd B can directly be buied from the market.
With 3; 5-dibromo pyridine 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid 6.3mmol; 0.27mmol tetra-triphenylphosphine palladium join in the reactor; vacuumize, after the logical nitrogen circulation 3 times; reaction system is under the nitrogen protection, and adding 50mL 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 24h.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: 71%.
Test result: MS:m/z 616 (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 383 ℃ among the embodiment of acquisition.
Recording electronic mobility by the field-effect transistor method is: 3.7 * 10 -4/ cm 2(Vs) -1
Embodiment two:
(4-(5-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridine-2-yl) phenyl)-its structural formula of 1H-benzoglyoxaline (25DPBiPy) is as follows for the organic semiconductor material 2-phenyl-1-that contains the benzoglyoxaline substituted pyridines of the present embodiment:
Figure BDA0000148736080000071
Above-mentioned 25DPBiPy material preparation step is as follows:
The preparation of 2-phenyl-1-(4-(5-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridine-2-yl) phenyl)-1H-benzoglyoxaline (25DPBiPy):
Figure BDA0000148736080000072
With 2; 5-dibromo pyridine 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid ester 6.0mmol; tetra-triphenylphosphine palladium 0.03mmol 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 xylene solution 50mL, 2mol/L 2CO 3Aqueous solution 35ml is heated to 120 ℃ 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: 75%.
Test result: MS:m/z 616 (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 382 ℃ among the embodiment of acquisition.
Recording electronic mobility by the field-effect transistor method is: 4.0 * 10 -4/ cm 2(Vs) -1
Embodiment three:
The organic semiconductor material 2-phenyl-1-that contains the benzoglyoxaline substituted pyridines of the present embodiment (4-(6-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridine-2-yl) phenyl)-1H-benzoglyoxaline (26DPBiPy), its structural formula is as follows:
Figure BDA0000148736080000081
Above-mentioned 26DPBiPy material preparation step is as follows:
The preparation of 2-phenyl-1-(4-(6-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridine-2-yl) phenyl)-1H-benzoglyoxaline (26DPBiPy):
Figure BDA0000148736080000082
With 2; 6-dibromo pyridine 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid 9.0mmol; tetra-triphenylphosphine palladium 0.01mmol 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 Li of toluene 50mL, 2mol/L 2CO 3Aqueous solution 34ml is heated to 115 ℃ of back flow reaction 20h 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: 74%.
Test result:
MS：m/z?616(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 379 ℃ among the embodiment of acquisition.
Recording electronic mobility by the field-effect transistor method is: 3.5 * 10 -4/ cm 2(Vs) -1
Embodiment four: the organic semiconductor material 2-phenyl-1-that contains the benzoglyoxaline substituted pyridines of the present embodiment (4-(4-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridine-2-yl) phenyl)-1H-benzoglyoxaline (24DPBiPy), and its structural formula is as follows:
Figure BDA0000148736080000091
Above-mentioned 24DPBiPy material preparation step is as follows:
The preparation of-phenyl-1-(4-(4-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridine-2-yl) phenyl)-1H-benzoglyoxaline (24DPBiPy):
Figure BDA0000148736080000092
With 2; 4-dibromo pyridine 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid ester 6.2mmol; tetra-triphenylphosphine palladium 0.09mmol 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 glycol dimethyl ether 55mL, 2mol/L 2CO 3Aqueous solution 34ml is heated to 100 ℃ of back flow reaction 24h 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: 70%.
Test result:
MS：m/z?616(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 378 ℃ among the embodiment of acquisition.
Recording electronic mobility by the field-effect transistor method is: 1.3 * 10 -4/ cm 2(Vs) -1
Embodiment five: the organic semiconductor material 2-phenyl-1-that contains the benzoglyoxaline substituted pyridines of the present embodiment (4-(5-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridin-3-yl) phenyl)-1H-benzoglyoxaline (35DPBiPy), and referring to embodiment one
With 3; 5-dibromo pyridine 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid 6.3mmol; three (dibenzalacetone) two palladium 0.15mmo join in the reactor; vacuumize, after the logical nitrogen circulation 3 times; reaction system is under the nitrogen protection, and adding 50mL 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 24h.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: 69%.
Test result: MS:m/z 616 (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 383 ℃ among the embodiment of acquisition.
Recording electronic mobility by the field-effect transistor method is: 3.7 * 10 -4/ cm 2(Vs) -1
Embodiment six: the organic semiconductor material 2-phenyl-1-that contains the benzoglyoxaline substituted pyridines of the present embodiment (4-(5-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridin-3-yl) phenyl)-1H-benzoglyoxaline (35DPBiPy), and referring to embodiment one
With 3; 5-dibromo pyridine 3mmol; [4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl] boric acid 6.3mmol; 0.06mmol two (triphenylphosphine) palladium chlorides join in the reactor; vacuumize, after the logical nitrogen circulation 3 times; reaction system is under the nitrogen protection, and adding 50mL 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 24h.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: 74%.
Test result: MS:m/z 616 (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 383 ℃ among the embodiment of acquisition.
Recording electronic mobility by the field-effect transistor method is: 3.7 * 10 -4/ cm 2(Vs) -1
See also Fig. 2, show and adopt the organic electroluminescence device that contains the organic semiconductor material of benzoglyoxaline substituted pyridines 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 is NPB (N, N '-two (Alpha-Naphthyl)-N, N '-phenylbenzene-4,4 '-diamines); Luminescent layer is MADN:DSA-Ph, wherein MADN is 2-methyl-9,10-two (naphthalene-2-yl) anthracene, DSA-Ph is 4-pair-[4-(N, N-phenylbenzene) amine] vinylbenzene-benzene, and it is 6wt% that MADN accounts for the luminescent layer total mass ratio, hole blocking layer 35 can be 2,9-dimethyl-4,7-phenylbenzene-9,10-phenanthroline (BCP); Electron transfer layer 36 is the organic semiconductor material of the benzoglyoxaline substituted pyridines in the embodiment of the invention; 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, electron transfer layer 36 is 2-phenyl-1-(4-(4-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridine-2-yl) phenyl)-1H-benzoglyoxaline (24DPBiPy), and the organic electroluminescence device representation is: ITO/NPB/MADN:DSA-Ph (6wt%)/BCP/24DPBiPy/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 4.7% external quantum efficiency.
Electroluminescent device luminous its maximum emission wavelength when voltage is 7.5V that should use-case belongs to dark blue smooth optical range at 460nm.
Fig. 3 contains the organic semiconductor material of benzoglyoxaline substituted pyridines 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, 2-phenyl-1-(4-(6-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridine-2-yl) phenyl) in the electron donor material employing embodiment of the invention three-1H-benzoglyoxaline, electron acceptor material can be [6,6] phenyl-C61-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/A1 or Ba/A1 etc.Wherein, glass-base 41 can be used as bottom, during making, choose ito glass, and after ultrasonic cleaning, process with oxygen-Plasma, supplementary layer 43 in the middle of ito glass applies on the supplementary layer 43, forms active coating 44 in the middle of the organic semiconductor material that contains the benzoglyoxaline substituted pyridines in the embodiment of the invention and electron acceptor material being coated on after by blend again, 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 3, under illumination, light transmission glass-base 41 and ITO electrode 42, the organic semiconductor material that contains the benzoglyoxaline substituted pyridines in the active coating 44 absorbs luminous energy, and produces exciton, these excitons move 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, the organic semiconductor material that contains the benzoglyoxaline substituted pyridines is shown 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), and insulation layer 52 can be but be not limited to micro-nano (such as 450nm) thick SiO 22-phenyl-1-(4-(6-(4-(2-phenyl-1H-benzoglyoxaline-1-yl) phenyl) pyridine-2-yl) phenyl) in the organic semiconductor layer 54 employing embodiment of the invention three-1H-benzoglyoxaline.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. an organic semiconductor material that contains the benzoglyoxaline substituted pyridines is characterized in that, the general formula of molecular structure of this material is as follows:
Figure FDA0000148736070000011
In the formula, Ar be H or
Figure FDA0000148736070000012
And Ar at least one be
2. a preparation method who contains the organic semiconductor material of benzoglyoxaline substituted pyridines is characterized in that, it comprises the steps:
Choose compd A and compd B, the chemical structural formula of compd A is as follows,
Figure FDA0000148736070000014
The chemical structural formula of compd B is as follows,
Figure FDA0000148736070000015
Or
Figure FDA0000148736070000016
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 containing the organic semiconductor material of benzoglyoxaline substituted pyridines, the structural formula of this material is as follows:
Figure FDA0000148736070000017
In the formula, Ar be H or
Figure FDA0000148736070000018
And Ar at least one be
3. the preparation method who contains the organic semiconductor material of benzoglyoxaline substituted pyridines as claimed in claim 2, 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.
4. the preparation method who contains the organic semiconductor material of benzoglyoxaline substituted pyridines as claimed in claim 2 is characterized in that, the temperature of described Suzuki coupling reaction is 70 ℃～120 ℃, and the time is 20～48h.
5. the preparation method who contains the organic semiconductor material of benzoglyoxaline substituted pyridines as claimed in claim 2 is characterized in that, the mole dosage of described compd A is 1: 2～1: 3 with the mole dosage of compd B ratio.
6. the preparation method who contains the organic semiconductor material of benzoglyoxaline substituted pyridines as claimed in claim 2 is characterized in that, described organic solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene and the toluene.
7. the preparation method who contains the organic semiconductor material of benzoglyoxaline substituted pyridines as claimed in claim 2 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.
8. an organic electroluminescence device comprises electron transfer layer, it is characterized in that, described electron transfer layer is the organic semiconductor material that contains the benzoglyoxaline substituted pyridines as claimed in claim 1.
9. a solar device comprises active coating, it is characterized in that, described active coating is the organic semiconductor material that contains the benzoglyoxaline substituted pyridines as claimed in claim 1.
10. an organic field effect tube comprises organic semiconductor layer, it is characterized in that, described organic semiconductor layer is the organic semiconductor material that contains the benzoglyoxaline substituted pyridines as claimed in claim 1.
CN2012100895012A 2012-03-30 2012-03-30 Organic semiconductor material containing benzimidazole substituted pyridine as well as preparation method and applications thereof Pending CN103360368A (en)

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JP2002038141A (en) * 2000-07-28 2002-02-06 Fuji Photo Film Co Ltd New condensed heterocyclic compound, luminous element material and luminous element using the same
CN1934213A (en) * 2004-03-08 2007-03-21 出光兴产株式会社 Material for organic electroluminescent device and organic electroluminescent device using the same
CN101384560A (en) * 2004-04-07 2009-03-11 出光兴产株式会社 Nitrogen-containing heterocyclic derivative and organic electroluminescent device using the same
CN101959867A (en) * 2007-12-27 2011-01-26 出光兴产株式会社 Nitrogen-containing heterocyclic derivative and organic electroluminescent element using same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002038141A (en) * 2000-07-28 2002-02-06 Fuji Photo Film Co Ltd New condensed heterocyclic compound, luminous element material and luminous element using the same
CN1934213A (en) * 2004-03-08 2007-03-21 出光兴产株式会社 Material for organic electroluminescent device and organic electroluminescent device using the same
CN101384560A (en) * 2004-04-07 2009-03-11 出光兴产株式会社 Nitrogen-containing heterocyclic derivative and organic electroluminescent device using the same
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Application publication date: 20131023