CN102329415B - Porphyrin-quinoxaline copolymer containing carbazole, preparation method thereof and application thereof - Google Patents

Porphyrin-quinoxaline copolymer containing carbazole, preparation method thereof and application thereof Download PDF

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CN102329415B
CN102329415B CN 201010226058 CN201010226058A CN102329415B CN 102329415 B CN102329415 B CN 102329415B CN 201010226058 CN201010226058 CN 201010226058 CN 201010226058 A CN201010226058 A CN 201010226058A CN 102329415 B CN102329415 B CN 102329415B
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porphyrin
quinoxaline
multipolymer
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carbazolyl
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CN102329415A (en
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周明杰
黄杰
刘贻锦
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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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Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention relates to a porphyrin-quinoxaline copolymer containing carbazole, a preparation method thereof and an application thereof. The structural formula of the copolymer is shown in the specification. In the structural formula, n is an integer between 1 and 100, and R1 and R2 are hydrogen or C1-C32 alkyl. The porphyrin-quinoxaline copolymer containing carbazole, which has the advantages of good dissolvability, wide spectral absorption range and high energy conversion efficiency, can be applied to fields of organic solar cell devices, organic electroluminescent devices, organic field effect transistor devices and the like as an organic semiconductor material.

Description

Contain carbazolyl porphyrin-quinoxaline multipolymer and its preparation method and application
[technical field]
The present invention relates to the organic semiconductor material field, relate in particular to a kind of carbazolyl porphyrin-quinoxaline multipolymer and its preparation method and application that contains.
[background technology]
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.Polymer materials is on the one hand because the environmental stability of organic materials is good, preparation cost is low, function is easy to modulation, snappiness and good film-forming property; On the other hand because the organic solar batteries course of processing is relatively simple, but cold operation, and the element manufacturing cost is the advantage such as lower and receiving much concern also, becomes cheap and attractive solar cell material.
Porphyrin Molecule is the general name that is connected with a substituent class macrocylc compound at porphin ring, and porphines is the large ring delocalizedπelectron of the two dimensional structure conjugated system that is replaced by the Dan Shuanjian that four pyrrole rings and four methyne bridgings get up.The quantum yield of their charge transfer and energy transfer reaction is higher, has good electronics resiliency and photoelectric magnetic property, good hard and soft property and better thermostability and environmental stability.Therefore, the porphyrin organic semiconductor material is the up-and-coming material of a class, and its application in the photovoltaic field has obtained broad research.
Carbazole is the good hole mobile material of a class: on the one hand, because the pi-conjugated effect of p-, the N atom on the carbazole is supplied with two keys with unshared-electron, makes two key electron riches; On the other hand, the N atom of parent electricity absorbs electronics on two keys by inductive effect again, and wherein conjugative effect is greater than inductive effect, so carbazole has very strong cavity transmission ability, and this just makes it that very large potential using value is arranged aspect organic semiconductor material.
Yet the effciency of energy transfer of traditional organic semiconductor material that contains carbazole or porphyrin is lower, has greatly limited the range of application of this class material.
[summary of the invention]
Based on this, be necessary to provide a kind of effciency of energy transfer higher contain carbazolyl porphyrin-quinoxaline multipolymer.
A kind of carbazolyl porphyrin-quinoxaline multipolymer that contains has following structural formula (III):
Figure BSA00000188829600021
Wherein, n is 1～100 integer; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
By introducing the group that increases solubility, for example alkyl can improve solubility and the film-forming properties of polymer materials, and can regulate and control the extinction scope of carbazolyl porphyrin.Therefore, the above-mentioned carbazolyl porphyrin-quinoxaline multipolymer that contains has good solubility, lower energy gap, wider spectral absorption scope, is conducive to current carrier and more effectively transmits in active layer material inside, and photoelectric transformation efficiency is high.
A kind of preparation method who contains carbazolyl porphyrin-quinoxaline multipolymer, in oxygen-free environment, with 5,15-two bromo-10,20-alkyl carbazole porphyrin or derivatives thereof (I) carries out the Stille coupling reaction with two tributyl tin-quinoxalines (II) under the catalysts and solvents existence condition, obtain containing carbazolyl porphyrin-quinoxaline multipolymer (III), reaction formula is as follows:
Figure BSA00000188829600022
Wherein, n is 1～100 integer; R 1And R 2Identical or not identical, be hydrogen or C 1～C 32Alkyl.
Wherein, 5,15-, two bromo-10,20-alkyl carbazole porphyrin (I) is 1: 1.5～1.5: 1 with the mol ratio of two tributyl tin-quinoxalines (II); Temperature of reaction is 50-130 ℃, and the time is 12～72 hours.
Wherein, catalyzer is the mixture of organic palladium and organophosphor ligand.
Wherein, organic palladium is Pd 2(dba) 3, Pd (OAc) 2, Pd (PPh 3) 4Or Pd (PPh 3) 2Cl 2In at least a; Organophosphor ligand is tricyclohexyl phosphine or P (o-Tol) 3In at least a; The mol ratio of organic palladium and organophosphor ligand is 1: 2～1: 20.
Wherein, the molar weight of catalyzer be two tributyl tin-quinoxalines (II) molar weight 0.05%～30%.
Wherein, solvent is at least a in benzene, toluene, glycol dimethyl ether, the tetrahydrofuran (THF).
Above-mentioned preparation method utilizes the Stille reaction principle, and technique is simple, low for equipment requirements.
A kind of organic solar batteries device, comprise successively glass baseplate, be located at conductive layer on the glass baseplate, be coated in poly-(3 on the conductive layer, the 4-Ethylenedioxy Thiophene): gather (styrene sulfonic acid) layer, be coated in poly-(3,4-Ethylenedioxy Thiophene): the active coating on poly-(styrene sulfonic acid) layer, the metal Al layer that is deposited on the active coating reach the Resins, epoxy that is used for encapsulating above-mentioned each layer.Active coating comprises electron donor material and electron acceptor material.Electron acceptor material is [6,6] phenyl-C 61-methyl-butyrate.Electron donor material is the aforesaid carbazolyl porphyrin-quinoxaline multipolymer that contains.
A kind of organic electroluminescence device comprises successively glass baseplate, is located at conductive layer on the glass baseplate, is coated in luminescent layer on the conductive layer, evaporation is at the LiF buffer layer on the luminescent layer and be deposited on metal Al layer on the LiF buffer layer.Luminescent layer is the aforesaid carbazolyl porphyrin-quinoxaline multipolymer that contains.
A kind of organic field effect tube device comprises successively the doped silicon wafer base material, is located at the SiO of doped silicon wafer substrate surface 2Insulation layer, be coated in described SiO 2The octadecyl trichlorosilane alkane decorative layer on surface, be coated in the organic semiconductor layer on the octadecyl trichlorosilane alkane decorative layer and source electrode and the drain electrode of organic semiconductor layer surface are set.Organic semiconductor layer is the aforesaid carbazolyl porphyrin-quinoxaline multipolymer that contains.
Above-mentioned polymer materials is high, easy to utilize as the photoelectric transformation efficiency of polymer solar cell device, organic electroluminescent device and the organic field effect tube device of active material preparation.
[description of drawings]
Fig. 1 is the structural representation of the organic solar batteries device that contains carbazolyl porphyrin-quinoxaline multipolymer of an embodiment.
Fig. 2 be an embodiment contain carbazolyl porphyrin-quinoxaline multipolymer as the structural representation of the organic electroluminescence device of luminescent layer.
Fig. 3 be an embodiment contain carbazolyl porphyrin-quinoxaline multipolymer as the structural representation of the organic field effect tube of organic semiconductor layer.
[embodiment]
Below mainly be further described with embodiment carbazolyl porphyrin-quinoxaline multipolymer and its preparation method and application that contains to present embodiment by reference to the accompanying drawings.
Carbazolyl porphyrin-quinoxaline the multipolymer that contains of present embodiment has following structural formula (III):
Figure BSA00000188829600041
Wherein, n is the integer between 1～100; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
By introducing the group that increases solubility, for example alkyl can improve solubility and the film-forming properties of polymer materials, and can regulate and control the extinction scope of carbazolyl porphyrin.Therefore, the above-mentioned carbazolyl porphyrin-quinoxaline multipolymer that contains has good solubility, lower energy gap, wider spectral absorption scope, is conducive to current carrier and more effectively transmits in active layer material inside, and photoelectric transformation efficiency is high.
The above-mentioned preparation process that contains carbazolyl porphyrin-quinoxaline multipolymer comprises the steps:
Step S1: following structural formula (I) and raw materials of compound (II) are provided:
Figure BSA00000188829600051
Wherein, R 1And R 2Be hydrogen or C 1～C 32Alkyl;
Step S2: in oxygen-free environment (oxygen-free environment of the present invention is comprised of nitrogen and/or rare gas element), with structural formula (I) and (II) compound under the catalysts and solvents existence condition, raw material is that 1: 1.5～1.5: 1 ratio is carried out the Stille coupling reaction in molar ratio under 50～130 ℃ of conditions, reacts obtained having structural formula in 12～72 hours multipolymer of (III);
Reaction formula is:
Figure BSA00000188829600052
Catalyzer can be the mixture of organic palladium or organic palladium and organophosphorus ligand.The consumption of catalyzer be structural formula (II) the compound molar weight 0.05%～30%.Wherein, organic palladium is Pd 2(dba) 3, Pd (OAc) 2, Pd (PPh 3) 4Or Pd (PPh 3) 2Cl 2Organophosphorus ligand is tricyclohexyl phosphine or P (o-Tol) 3In at least a.When catalyzer was the mixture of organic palladium and organophosphorus ligand, the mol ratio of organic palladium and organophosphorus ligand was 1: 2～20.
Preferably, solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene or the toluene.
After the crude product in solution that obtains the Stille coupled reaction, also need crude product in solution is carried out sedimentation, drying treatment: at first, solution is added drop-wise in the methyl alcohol, carries out sedimentation and process, suction filtration then, methanol wash, drying must contain assorted copolymer colloid; With the toluene dissolving, get the toluene solution of multipolymer subsequently; Then, this toluene solution is joined in the aqueous solution of Thiocarb, 90 ℃ of heated and stirred mixed solutions with the column chromatography of mixed solution by aluminum oxide, are isolated multipolymer, then chlorobenzene drip washing, and organic solvent is removed in subsequently decompression; Repeat above-mentioned sedimentation treatment step, and extract multipolymer with the acetone Soxhlet, obtain copolymer solids.
Above-mentioned preparation method utilizes the Stille reaction principle, and technique is simple, low for equipment requirements.
Further specify the above-mentioned carbazolyl porphyrin-quinoxaline multipolymer and its preparation method and application that contains below by specific embodiment.
Embodiment 1
Present embodiment disclose a kind of structure following 10,20-two (9-octyl group carbazole) porphyrin-quinoxaline multipolymer:
Figure BSA00000188829600061
The preparation process of above-mentioned multipolymer is as follows:
Step S11, synthetic 5,8-, two bromo-2, two (phenyl) quinoxalines of 3-, reaction formula is as follows:
Figure BSA00000188829600062
At 120 ℃ 3,6-, two bromo-O-Phenylene Diamines (1.01g, 3.7mmol) are joined in the acetic acid solution of 20ml diphenylthanedione (0.39g, 1.8mmol).Backflow is spent the night, and reaction solution is poured into water, and is neutralized to neutrality with sodium bicarbonate.Chloroform extraction, saturated common salt water washing, anhydrous sodium sulfate drying.The rotary evaporation desolventizing, thick product column chromatography gets white solid.Then be to obtain the white solid powder with chloroform/normal hexane recrystallization.The productive rate 86% of above-mentioned reaction.
Step S12, synthetic 5,8-two (tributyl tin)-2, two (phenyl) quinoxalines of 3-, reaction formula is as follows:
Figure BSA00000188829600071
In the 500ml there-necked flask, add 5,8-, two bromo-2, two (phenyl) quinoxaline (1.32g of 3-, 3mmol), the 300ml tetrahydrofuran (THF) is cooled to system-30 ℃, drip the n-Butyl Lithium 2.5ml of 2.5mol/L, then at-30 ℃ of reactions 1h, again property adding SnBu 3Cl (2.08g, 6.4mmol) at-30 ℃ of reaction 30min, then is warming up to room temperature naturally, and stirring reaction spends the night.Reactant is poured in the frozen water, used extracted with diethyl ether, anhydrous magnesium sulfate drying, the underpressure distillation desolventizing is carried out column chromatography for separation with silica gel/sherwood oil (30～60 ℃), obtains product, productive rate 89.0%.
Step S13, synthetic 5,15-two (9-octyl group carbazole) porphyrin, reaction formula is as follows:
Figure BSA00000188829600072
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde-9-octyl group carbazole (0.31g, 1mmol) and dipyrrylmethanes (0.15g, 1mmol), be dissolved in the 250ml methylene dichloride.Pass into nitrogen 30min, use syringe to add propionic acid 1ml, then 20 ℃ of lower 24h that stir add DDQ (DDQ) (0.91g, 4mmol), and 30min is at room temperature stirred in continuation.Then add the 1ml triethylamine and carry out the cancellation reaction, concentrated solvent filters, and collects filtrate and is spin-dried for solvent, with methylene dichloride fast drip washing on silicagel column, is spin-dried for solvent, and to product, productive rate is about 86.4% with ether/recrystallizing methanol.
Step S14, synthetic 5,15-, two bromo-10,20-two (9-octyl group carbazole) porphyrin, reaction formula is as follows:
Figure BSA00000188829600081
Put up the anhydrous and oxygen-free device, take by weighing 5,15-two (9-octyl group carbazole) porphyrin (0.17g, 0.2mmol) be dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃, add N-bromo-succinimide (0.07g, 0.4mmol), behind the stirring 72h, mixture returns to room temperature.Then continue to stir 4h, add 5ml acetone termination reaction, desolventizing is carried out recrystallization with ether/methyl alcohol and is obtained product 0.18g, productive rate 88.2%.
Step S15, synthetic 10,20-two (9-octyl group carbazole) porphyrin-quinoxaline multipolymer, reaction formula is as follows:
Figure BSA00000188829600082
Under nitrogen protection; add 5; 8-two (tributyl tin)-2; two (phenyl) quinoxalines (172mg, 0.2mmol), 5 of 3-, 15-two bromo-10; 20-two (9-octyl group carbazole) porphyrin (204mg; 0.2mmol) and toluene solvant 80ml, vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh 3) 2Cl 2, be heated to 100 ℃ of reaction 56h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 250ml methyl alcohol.Suction filtration, methanol wash, drying.Then with the toluene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone apparatus,Soxhlet's.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 80.1%.Molecular weight (GPC, THF, R.I): M n=38100, M w/ M n=3.37.
Embodiment 2
Present embodiment discloses the following 10-of a kind of structure (9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin quinoxaline multipolymer:
Figure BSA00000188829600091
The preparation process of above-mentioned multipolymer is as follows:
Step S21, synthetic 5,8-two (tributyl tin)-2, two (phenyl) quinoxalines of 3-.
Its preparation method is with step S11, the step S 12 of embodiment 1.
Step S22, synthetic 5-(9-methyl carbazole)-15-(9-dotriacontyl carbazole) porphyrin, reaction formula is as follows:
Figure BSA00000188829600101
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde-9-methyl carbazole (0.21g, 1mmol), 2-aldehyde-9-dotriacontyl carbazole (0.65g, 1mmol), dipyrrylmethanes (0.30g, 2mmol), be dissolved in the 250ml methylene dichloride.Pass into nitrogen 30min, use syringe to add trifluoroacetic acid 2ml, 100 ℃ of lower 1h that stir.Then add DDQ (DDQ) (1.82g, 8mmol), continue at room temperature to stir 30min.Then add 2ml pyridine cancellation reaction, concentrated solvent filters, and collects filtrate and is spin-dried for solvent, with methylene dichloride fast drip washing on silicagel column, is spin-dried for solvent, and to product, productive rate is about 74.3% with ether/recrystallizing methanol.
Step S23, synthetic 5,15-, two bromo-10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin, reaction formula is as follows:
Figure BSA00000188829600102
Put up the anhydrous and oxygen-free device, take by weighing 5-(9-methyl carbazole)-15-(9-dotriacontyl carbazole) porphyrin (0.22g, 0.2mmol) and be dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃.Add N-bromo-succinimide (0.07g, 0.4mmol), behind the stirring 0.5h, mixture is warming up to 120 ℃, after then continuing to stir 1h, adds 5ml acetone termination reaction, and desolventizing is carried out recrystallization with ether/methyl alcohol and obtained product, productive rate 83.3%.
Step S24, synthetic 10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin quinoxaline multipolymer, reaction formula is as follows:
Figure BSA00000188829600111
Mixed gas protected lower at nitrogen and argon gas; add 5; 8-two (tributyl tin)-2; two (phenyl) quinoxaline (172mg of 3-; 0.2mmol), 5,15-two bromo-10,20-two (9-octyl group carbazole) porphyrin (252mg; 0.2mmol) and toluene solvant 80ml, vacuumize deoxygenation and be filled with nitrogen and the argon gas mixed gas.Then add Pd (OAc) 2(2.5mg)/tricyclohexyl phosphine (6.5mg) and 2ml 20% (wt) Et 4NOH solution is heated to 120 ℃ of reaction 24h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 250ml methyl alcohol.Suction filtration, methanol wash, drying.Then with the toluene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone apparatus,Soxhlet's.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 78.3%.Molecular weight (GPC, THF, R.I): M n=34100, M w/ M n=3.64.
Embodiment 3
Present embodiment discloses the following 10-carbazole-20-of a kind of structure (9-hexadecyl carbazole) porphyrin quinoxaline multipolymer:
Figure BSA00000188829600121
The preparation process of above-mentioned multipolymer is as follows:
Step S31, synthetic 5,8-two (tributyl tin)-2, two (phenyl) quinoxalines of 3-.
Its preparation is with embodiment 1 step S11, S12.
Step S32, synthetic 5-carbazole-15-(9-hexadecyl carbazole) porphyrin, reaction formula is as follows:
Figure BSA00000188829600122
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde carbazole (0.20g, 1mmol), 2 aldehyde-9-hexadecyl carbazole (0.42g, 1mmol), dipyrrylmethanes (0.30g, 2mmol), be dissolved in the 300ml methylene dichloride.Pass into nitrogen 30min, syringe adds trifluoroacetic acid 2ml, stirs 3h under the room temperature, then add DDQ (DDQ) (1.82g, 8mmol), continue at room temperature to stir 30min, then add the 2ml triethylamine and carry out the cancellation reaction, concentrated solvent filters, and collects filtrate and is spin-dried for solvent, with methylene dichloride fast drip washing on silicagel column, be spin-dried for solvent, to product, productive rate is about 86.8% with ether/recrystallizing methanol.
Step S33, synthetic 5,15-, two bromo-10-carbazole-20-(9-hexadecyl carbazole) porphyrin, reaction formula is as follows:
Figure BSA00000188829600131
Put up the anhydrous and oxygen-free device, take by weighing 5-carbazole-15-(9-hexadecyl carbazole) porphyrin (0.17g, 0.2mmol) and be dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃.Add N-bromo-succinimide (0.07g, 0.4mmol), behind the stirring 0.5h, mixture is warming up to 30 ℃, then continues to stir 48h, adds 5ml acetone termination reaction, and desolventizing is carried out recrystallization with ether/methyl alcohol and obtained product, productive rate 78.2%.
Step S34, synthetic 10-carbazole-20-(9-hexadecyl carbazole) porphyrin quinoxaline multipolymer, reaction formula is as follows:
Figure BSA00000188829600132
Under argon shield; add 5; 8-two (tributyl tin)-2; two (phenyl) quinoxaline (172mg of 3-; 0.2mmol), 5; 15-two bromo-10-carbazole-20-(9-hexadecyl carbazole) porphyrin (205mg, 0.2mmol) and toluene solvant 100ml vacuumize deoxygenation and are filled with argon gas.Then add 8mg Pd (PPh 3) 4, be heated to 50 ℃ of reaction 72h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 300ml methyl alcohol.Suction filtration, methanol wash, drying.Then with the toluene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 73.9%.Molecular weight (GPC, THF, R.I): M n=35200, M w/ M n=3.38.
Embodiment 4
With 10 of embodiment 1,20-two (9-octyl group carbazole) porphyrin-quinoxaline multipolymer is as the organic solar batteries device of active layer material, and its structure as shown in Figure 1.
Active layer material comprises above-mentioned multipolymer as electron donor material, [6,6] phenyl-C 61-methyl-butyrate (being called for short PCBM) is as electron acceptor material, be that device architecture is glass/ITO/PEDOT:PSS/ active coating/Al, wherein ITO is that square resistance is the tin indium oxide of 10-20 Ω/, PEDOT is poly-(3, the 4-Ethylenedioxy Thiophene), PSS is poly-(styrene sulfonic acid); Ito glass is through after the ultrasonic cleaning, process with oxygen-Plasma, coat PEDOT:PSS at ITO, active coating adopts spin coating technique as electron donor material and PCBM as electron acceptor material with multipolymer of the present invention, metal aluminium electrode prepares by vacuum evaporation technology, obtains the organic solar batteries device.With device with epoxy encapsulation after, place under 110 ℃ of air tight conditions annealing 4 hours, drop to again room temperature.Because after device was annealed, the chemical structure of material was more regular in order, has improved transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Embodiment 5
With 10 of embodiment 1, porphyrin-quinoxaline multipolymer is as the luminescent layer organic electroluminescence device for 20-two (9-octyl group carbazole), and its structure as shown in Figure 2.
This device is followed successively by glass/ITO/ multipolymer/LiF/Al of the present invention, be that the tin indium oxide (ITO) of 10-20 Ω/mouth is as transparent anode at glass substrate deposition one deck square resistance namely, prepare one deck copolymer material of the present invention as luminescent layer by spin coating technique at ITO, vacuum evaporation LiF on this luminescent layer again, as buffer layer, adopt vacuum coating technology metal refining Al at buffer layer at last, as the negative electrode of device.
Embodiment 6
Containing 10 of embodiment 1, the organic field effect tube of 20-two (9-octyl group carbazole) porphyrin-quinoxaline multipolymer, its structure is as shown in Figure 3.
Adopt highly doped silicon chip (Si) as substrate, the SiO that 450nm is thick 2As insulation layer, source electrode (S) and drain electrode (D) all adopt gold or copper as electrode, and multipolymer of the present invention is spun to SiO after octadecyl trichlorosilane alkane (OTS) is modified as organic semiconductor layer 2On, thereby make the organic field effect tube that contains 10,20-two (9-octyl group carbazole) porphyrin-quinoxaline multipolymer.
High, easy to utilize as the photoelectric transformation efficiency of polymer solar cell device, organic electroluminescent device and the organic field effect tube device of active material preparation with above-mentioned polymer materials.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a multipolymer that contains carbazolyl porphyrin-quinoxaline is characterized in that, has following structural formula (III):
Figure FSB00000975863800011
Wherein, n is 1～100 integer; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
2. preparation method who contains the multipolymer of carbazolyl porphyrin-quinoxaline, it is characterized in that, in oxygen-free environment, with 5,15-two bromo-10,20-alkyl carbazole porphyrin or derivatives thereof (I) carries out the Stille coupling reaction with two tributyl tin-quinoxalines (II) under the catalysts and solvents existence condition, obtain containing the multipolymer (III) of carbazolyl porphyrin-quinoxaline, and reaction formula is as follows:
Figure FSB00000975863800012
Wherein, n is 1～100 integer; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
3. the preparation method who contains the multipolymer of carbazolyl porphyrin-quinoxaline according to claim 2, it is characterized in that: described 5,15-two bromo-10,20-alkyl carbazole porphyrin (I) is 1: 1.5～1.5: 1 with the mol ratio of described pair of tributyl tin-quinoxaline (II); Described Stille coupling reaction temperature is 50-130 ℃, and the reaction times is 12～72 hours.
4. the preparation method who contains the multipolymer of carbazolyl porphyrin-quinoxaline according to claim 2, it is characterized in that: described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand.
5. the preparation method who contains the multipolymer of carbazolyl porphyrin-quinoxaline according to claim 4, it is characterized in that: described organic palladium is Pd 2(dba) 3, Pd (OAc) 2, Pd (PPh 3) 4Or Pd (PPh 3) 2Cl 2In at least a; Described organophosphor ligand is tricyclohexyl phosphine or P (o-Tol) 3In at least a; The mol ratio of described organic palladium and described organophosphor ligand is l: 2～1: 20.
6. it is characterized in that according to claim 2 or the 4 or 5 described preparation methods that contain the multipolymer of carbazolyl porphyrin-quinoxaline: the molar weight of described catalyzer be described pair of tributyl tin-quinoxaline (II) molar weight 0.05%～30%.
7. the preparation method who contains the multipolymer of carbazolyl porphyrin-quinoxaline according to claim 2 is characterized in that: described solvent is at least a in benzene, toluene, glycol dimethyl ether, the tetrahydrofuran (THF).
8. organic solar batteries device, comprise successively glass baseplate, be located at conductive layer on the described glass baseplate, be coated in poly-(3 on the described conductive layer, the 4-Ethylenedioxy Thiophene): gather (styrene sulfonic acid) layer, be coated in described poly-(3, the 4-Ethylenedioxy Thiophene): the active coating on poly-(styrene sulfonic acid) layer, the metal Al layer that is deposited on the described active coating reach the Resins, epoxy that is used for encapsulating above-mentioned each layer, described active coating comprises electron donor material and electron acceptor material, described electron acceptor material is [6,6] phenyl-C 61-methyl-butyrate is characterized in that, described electron donor material is for having the multipolymer that contains carbazolyl porphyrin-quinoxaline of structural formula (III):
Figure FSB00000975863800021
Wherein, n is 1～100 integer; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
9. organic electroluminescence device, comprise successively glass baseplate, be located at conductive layer on the described glass baseplate, be coated in luminescent layer on the described conductive layer, evaporation is at the LiF buffer layer on the described luminescent layer and be deposited on metal Al layer on the described LiF buffer layer, it is characterized in that described luminescent layer is for having the multipolymer that contains carbazolyl porphyrin-quinoxaline of structural formula (III):
Figure FSB00000975863800031
Wherein, n is 1～100 integer; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
10. organic field effect tube device comprises successively the doped silicon wafer base material, is located at the SiO of described doped silicon wafer substrate surface 2Insulation layer, be coated in described SiO 2The octadecyl trichlorosilane alkane decorative layer on surface, be coated in the organic semiconductor layer on the described octadecyl trichlorosilane alkane decorative layer and source electrode and the drain electrode of organic semiconductor layer surface are set, it is characterized in that described organic semiconductor layer is for having the multipolymer that contains carbazolyl porphyrin-quinoxaline of structural formula (III):
Figure FSB00000975863800032
Wherein, n is 1～100 integer; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
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