CN102329417A - Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof - Google Patents

Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof Download PDF

Info

Publication number
CN102329417A
CN102329417A CN2010102261258A CN201010226125A CN102329417A CN 102329417 A CN102329417 A CN 102329417A CN 2010102261258 A CN2010102261258 A CN 2010102261258A CN 201010226125 A CN201010226125 A CN 201010226125A CN 102329417 A CN102329417 A CN 102329417A
Authority
CN
China
Prior art keywords
benzene
layer
porphyrin
organic
carbazole porphyrin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2010102261258A
Other languages
Chinese (zh)
Other versions
CN102329417B (en
Inventor
周明杰
黄杰
刘贻锦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=45481401&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN102329417(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN 201010226125 priority Critical patent/CN102329417B/en
Publication of CN102329417A publication Critical patent/CN102329417A/en
Application granted granted Critical
Publication of CN102329417B publication Critical patent/CN102329417B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention relates to a copolymer containing carbazole porphyrin-benzene, which has a structural formula shown as below, wherein n is an integer from 1 to 100, and R1 and R2 are hydrogen or C1-C32 alkyl. The copolymer containing carbazole porphyrin-benzene has good solubility, a broader spectral absorption range and higher energy conversion efficiency and can be used as an organic semiconductor material in solar cells, organic electroluminescent devices, organic field effect transistors and other fields.

Description

Contain carbazole porphyrin-benzene multipolymer
[technical field]
The present invention relates to the organic semiconductor material field, relate in particular to a kind of carbazole porphyrin-benzene multipolymer that contains.
[background technology]
Utilize cheap material preparation low cost, dynamical solar cell is photovoltaic hot research fields and difficult point 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 simple relatively, but cold operation, and advantage such as the element manufacturing cost is also lower and receiving much concern becomes cheap and attractive solar cell material.
The porphyrin molecule is the general name that on porphin ring, is connected with substituent one type of macrocylc compound, and porphines is by four pyrrole rings and four the big ring delocalized of Dan Shuanjian alternative two dimensional structure conjugated systems that the methyne bridging gets up.The quantum yield of their charge transfer and energy transfer reaction is higher, has good electron resiliency and photoelectric magnetic property, good hard and soft property and better thermostability and environmental stability.Therefore, porphyrin class organic semiconductor material is one type of up-and-coming material, and its application in the photovoltaic field has obtained broad research.
Carbazole is one type of good cavity transport material: on the one hand, because the pi-conjugated effect of p-, the N atom on the carbazole not shared electron is supplied with two keys, makes two key electron riches; On the other hand, the N atom of parent electricity absorbs the electronics on two keys through 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 big 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, big limitations the range of application of this type material.
[summary of the invention]
Based on this, be necessary to provide a kind of energy conversion efficiency higher contain carbazole porphyrin-benzene multipolymer.
A kind of carbazole porphyrin-benzene multipolymer that contains has following structural formula (III):
Wherein, n is the integer between 1-100; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
Through introduce increasing the group of solubility, alkyl for example can improve the solubility and the film-forming properties of polymer materials and the extinction scope of adjustable carbazole porphyrin.Therefore, the above-mentioned carbazole porphyrin-benzene multipolymer that contains has good solubility, lower energy gap, the spectral absorption scope of broad, helps current carrier and more effectively transmits in active layer material inside, and photoelectric transformation efficiency is high.
A kind of preparation method who contains carbazole porphyrin-benzene multipolymer; Be in oxygen-free environment; With 5,15-two bromo-10,20-alkyl carbazole porphyrin or derivatives thereof (I) is carrying out the Suzuki coupling reaction with two boric acid ester benzene (II) under catalyzer and solvent existence condition; Obtain containing carbazole porphyrin-benzene multipolymer (III), reaction formula is following:
Figure BSA00000189030500022
Wherein, n is the integer between 1-100; R 1And R 2Identical or inequality, be hydrogen or C 1～C 32Alkyl.
Wherein, 5,15-two bromo-10,20-alkyl carbazole porphyrin is 1: 1.5～1.5: 1 with the mol ratio of two boric acid ester benzene; Temperature of reaction is 50-120 ℃, and the reaction times is 24～72 hours.
Wherein, catalyzer is the mixture for organic palladium or 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 boric acid ester benzene (II) molar weight 0.05%～20%.
Wherein, solvent is at least a in benzene, toluene, glycol dimethyl ether, the THF.
Above-mentioned preparation method utilizes the Suzuki reaction principle, and technology is simple, low for equipment requirements.
A kind of organic solar batteries device; Comprise glass baseplate successively, be located at conductive layer on the glass baseplate, be coated in and gather (3 on the conductive layer; The 4-Ethylenedioxy Thiophene), gather (styrene sulfonic acid) layer, be coated in and gather (3, the 4-Ethylenedioxy Thiophene), gather active coating on (styrene sulfonic acid) layer, be deposited on the metal Al layer on the active coating and be used to encapsulate the epoxy resin of above-mentioned each layer.Active coating comprises electron donor material and electron acceptor material, and electron acceptor material is [6,6] phenyl-C 61-methyl-butyrate.Electron donor material is the aforesaid carbazole porphyrin-benzene multipolymer that contains.
A kind of organic electroluminescence device comprises glass baseplate successively, is located at conductive layer on the glass baseplate, is coated in luminescent layer on the conductive layer, vapor deposition is at the LiF impact plies on the luminescent layer and be deposited on the metal Al layer on the LiF impact plies.Wherein, luminescent layer is the aforesaid carbazole porphyrin-benzene multipolymer that contains.
A kind of organic field effect tube device comprises the doped silicon wafer base material successively, is located at the SiO of doped silicon wafer substrate surface 2Insulation layer, be coated in SiO 2The octadecyl trichlorosilane decorative layer on surface, be coated in the organic semiconductor layer on the octadecyl trichlorosilane decorative layer and the source electrode and the drain electrode of organic semiconductor layer surface are set.Wherein, organic semiconductor layer is the aforesaid carbazole porphyrin-benzene 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 carbazole porphyrin-benzene multipolymer of an embodiment.
Fig. 2 be an embodiment contain the structural representation of carbazole porphyrin-benzene multipolymer as the organic electroluminescence device of luminescent layer.
Fig. 3 be an embodiment contain the structural representation of carbazole porphyrin-benzene multipolymer as the organic field effect tube of organic semiconductor layer.
[embodiment]
Mainly combine below accompanying drawing and embodiment to above-mentioned contain carbazole porphyrin-benzene multipolymer and its production and application be further described.
Carbazole porphyrin-benzene the multipolymer that contains of this embodiment has following structural formula (III):
Figure BSA00000189030500041
Wherein, n is the integer between the 1-100; R 1And R 2Be hydrogen or C 1-C 32Alkyl.
Through introduce increasing the group of solubility, alkyl for example can improve the solubility and the film-forming properties of polymer materials and the extinction scope of adjustable carbazole porphyrin.Therefore, the above-mentioned carbazole porphyrin-benzene multipolymer that contains has good solubility, lower energy gap, the spectral absorption scope of broad, helps current carrier and more effectively transmits in active layer material inside, and photoelectric transformation efficiency is high.
The above-mentioned preparation process that contains carbazole porphyrin-benzene multipolymer comprises the steps:
Step S1: following structural formula (I) and raw materials of compound (II) are provided:
Figure BSA00000189030500051
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 made up of nitrogen and/or rare gas element); With structural formula (I) and (II) compound be that 1: 1.5～1.5: 1 ratio is carried out the Suzuki coupling reaction in molar ratio under 50～120 ℃ of conditions at raw material under catalyzer and the solvent existence condition, react obtained having structural formula in 24～72 hours multipolymer of (III);
Reaction formula is:
Figure BSA00000189030500052
Catalyzer can be the mixture of organic palladium or organic palladium and organophosphorus ligand.Catalyst consumption be structural formula (II) the compound molar weight 0.05%～20%.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 THF, glycol dimethyl ether, benzene or the toluene.
After the crude product in solution that obtains the Suzuki coupled reaction, also need carry out sedimentation, drying treatment to crude product in solution: at first, drips of solution is added in the methyl alcohol, carries out sedimentation and handle, 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 through aluminum oxide, are isolated multipolymer, chlorobenzene drip washing then, and organic solvent is removed in decompression subsequently; Repeat the above-mentioned the first step, and extract multipolymer, obtain copolymer solids with acetone Suo Shi.
Above-mentioned preparation method utilizes the Suzuki reaction principle, and technology is simple, low for equipment requirements.
Further specify the above-mentioned carbazole porphyrin-benzene multipolymer that contains through specific embodiment below.
Embodiment 1
. present embodiment disclose a kind of structure following 10,20-two (9-octyl group carbazole) porphyrin-benzene multipolymer:
Figure BSA00000189030500061
The preparation process of above-mentioned multipolymer is following:
Step S11, synthetic 1,4-is to two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes), and reaction formula is following:
Figure BSA00000189030500062
Under protection of nitrogen gas, (4.8g 0.02mol), adds the tetrahydrofuran solvent of 100ml to add paradibromobenzene in the there-necked flask; (16.8mL 0.04mol), continues stirring reaction 2h, under-78 ℃ of conditions, injects 2-isopropoxy-4 with syringe under-78 ℃ of conditions, slowly to inject n-Butyl Lithium with syringe again; 4,5,5-tetramethyl--1,3; 2-two assorted oxygen pentaboranes (8.7mL, 0.04mol), stirred overnight under the room temperature.Add 30ml saturated sodium-chloride water solution termination reaction, use chloroform extraction, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve steaming and fall solvent.At last crude product is separated for leacheate carries out silica gel column chromatography with petrol ether/ethyl acetate (15/1), obtain product, productive rate 94.6%.
Step S12, synthetic 5,15-two (9-octyl group carbazole) porphyrin, reaction formula is following:
Put up the anhydrous and oxygen-free device, take by weighing midbody 2-aldehyde-9-octyl group carbazole (0.31g, 1mmol) with two pyrroles's methane (0.15g, 1mmol); Be dissolved in the 250ml methylene dichloride, feed nitrogen 30min, syringe adds propionic acid 1ml, and 20 ℃ are stirred 24h down; (0.91g 4mmol), continues at room temperature to stir 30min, adds 1ml triethylamine cancellation reaction then to add DDQ (DDQ) then; Concentrated solvent filters, and collects filtrating and revolves dried solvent, with methylene dichloride drip washing fast on silicagel column; Revolve dried solvent, to product, productive rate is about 86.4% with ether/recrystallizing methanol.
Step S13, synthetic 5,15-two bromo-10,20-two (9-octyl group carbazole) porphyrin, reaction formula is following:
Figure BSA00000189030500081
Put up the anhydrous and oxygen-free device, take by weighing 10, (0.17g 0.2mmol) is dissolved in the 80ml chloroform 20-two (9-octyl group carbazole) porphyrin; Add the 1ml pyridine, reactant is dropped to 0 ℃, and adding N-bromo-succinimide (0.07g, 0.4mmol); After stirring 72h, mixture returns to room temperature, continues to stir 4h then, adds 5ml acetone termination reaction; Remove and desolvate, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 88.2%.
Step S14, synthetic 10,20-two (9-octyl group carbazole) porphyrin-benzene multipolymer, reaction formula is following:
Figure BSA00000189030500082
Under nitrogen protection, add 1,4-two (4,4,5; 5-tetramethyl--1,3, assorted oxygen pentaboranes of 2-two) benzene (66mg, 0.2mmol), 5,15-two bromo-10; (205mg 0.2mmol) with toluene solvant 50ml, vacuumizes deoxygenation and charges into nitrogen 20-two (9-octyl group carbazole) porphyrin, adds 5mg Pd (PPh then 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 300ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirred overnight.With the column chromatography of organic phase through 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 80.9%, molecular weight (GPC, THF, R.I): M n=34600, M w/ M n=3.28).
Embodiment 2
Present embodiment discloses the following 10-of a kind of structure (9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin-benzene multipolymer:
The preparation process of above-mentioned multipolymer is following:
Step S21, synthetic 1,4-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) benzene.
Its preparation method is with the step S11 of embodiment 1.
Step S22, synthetic 5-(9-methyl carbazole)-10-(9-dotriacontyl carbazole) porphyrin, reaction formula is following:
Figure BSA00000189030500092
Put up the anhydrous and oxygen-free device, take by weighing midbody 2-aldehyde-9-methyl carbazole (0.21g, 1mmol), 2-aldehyde-9-dotriacontyl carbazole (0.65g, 1mmol), two pyrroles's methane (0.30g; 2mmol), be dissolved in the 250ml methylene dichloride, feed nitrogen 30min, syringe adds trifluoroacetic acid 2ml; 100 ℃ are stirred 1h down, and (1.82g 8mmol), continues at room temperature to stir 30min to add DDQ (DDQ) then; Add 2ml pyridine cancellation reaction then, concentrated solvent filters, and collects filtrating and revolves dried solvent; With methylene dichloride drip washing fast on silicagel column, revolve dried solvent, 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 following:
Figure BSA00000189030500101
Put up the anhydrous and oxygen-free device, (0.22g 0.2mmol) is dissolved in the 80ml chloroform, adds the 1ml pyridine to take by weighing 10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin; Reactant is dropped to 0 ℃, and adding N-bromo-succinimide (0.07g, 0.4mmol), behind the stirring 0.5h; Mixture is warming up to 120 ℃, after continuing then to stir 1h, adds 5ml acetone termination reaction; Remove and desolvate, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 83.3%.
Step S24, synthetic 10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin-benzene multipolymer, reaction formula is following:
Figure BSA00000189030500111
Mixed gas protected down at nitrogen and argon gas, add 1,4-two (4,4; 5,5-tetramethyl--1,3; The assorted oxygen pentaboranes of 2-two) benzene (66mg, 0.2mmol), 5,15-two bromo-10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin (253mg; 0.2mmol) and toluene solvant 120ml, vacuumize deoxygenation and charge into nitrogen and the argon gas mixed gas, add Pd (OAc) then 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 200ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 79.8%, molecular weight (GPC, THF, R.I): M n=36400, M w/ M n=3.57).
Embodiment 3
Present embodiment discloses the following 10-carbazole-20-of a kind of structure (9-hexadecyl carbazole) porphyrin-benzene multipolymer:
Figure BSA00000189030500121
The preparation process of above-mentioned multipolymer is following:
Step S31, synthetic 1,4-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) benzene.
Its preparation is with embodiment 1 step S11.
Step S32, synthetic 10-carbazole-20-(9-hexadecyl carbazole) porphyrin, reaction formula is following:
Figure BSA00000189030500122
Put up the anhydrous and oxygen-free device, take by weighing midbody 2-aldehyde carbazole (0.20g, 1mmol), 2 aldehyde-9-hexadecyl carbazole (0.42g, 1mmol), two pyrroles's methane (0.30g; 2mmol), be dissolved in the 300ml methylene dichloride, feed nitrogen 30min, syringe adds trifluoroacetic acid 2ml; Stir 3h under the room temperature, (1.82g 8mmol), continues at room temperature to stir 30min to add DDQ (DDQ) then; Add 2ml triethylamine cancellation reaction then, concentrated solvent filters, and collects filtrating and revolves dried solvent; With methylene dichloride drip washing fast on silicagel column, revolve dried 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 following:
Put up the anhydrous and oxygen-free device, (0.17g 0.2mmol) is dissolved in the 80ml chloroform, adds the 1ml pyridine to take by weighing 10-carbazole-20-(9-hexadecyl carbazole) porphyrin; Reactant is dropped to 0 ℃, and adding N-bromo-succinimide (0.07g, 0.4mmol), behind the stirring 0.5h; Mixture is warming up to 30 ℃, continues to stir 48h then, adds 5ml acetone termination reaction; Remove and desolvate, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 78.2%.
Step S34, synthetic 10-carbazole-20-(9-hexadecyl carbazole) porphyrin-benzene multipolymer, reaction formula is following:
Figure BSA00000189030500132
Under argon shield, add 1,4-two (4,4; 5,5-tetramethyl--1,3; The assorted oxygen pentaboranes of 2-two) benzene (66mg, 0.2mmol), 5,15-two bromo-10-carbazole-20-(9-hexadecyl carbazole) porphyrin (205mg; 0.2mmol) and toluene solvant 100ml, vacuumize deoxygenation and charge into argon gas, add 10mg Pd (PPh then 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.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 84.1%.Molecular weight (GPC, THF, R.I): M n=38700, M w/ M n=3.29).
Embodiment 4
With 10 of embodiment 1,20-two (9-octyl group carbazole) porphyrin-benzene multipolymer is as the organic solar batteries device of active layer material, and its structure is 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/, and PEDOT is for gathering (3; The 4-Ethylenedioxy Thiophene), PSS is for gathering (styrene sulfonic acid); Ito glass is through after the ultrasonic cleaning; Handle with oxygen-Plasma, on ITO, coat PEDOT:PSS, active coating adopts spin coating technique as electron donor material and PCBM as electron acceptor material with P1; Metal aluminium electrode obtains the organic solar batteries device through the vacuum evaporation technology preparation.With device with epoxy encapsulation after, place under 110 ℃ of air tight conditions annealing 4 hours, drop to room temperature again.Because after device was annealed, the chemical structure of material was more regular in order, has improved the transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Embodiment 5
With 10 of embodiment 1,20-two (9-octyl group carbazole) porphyrin-benzene multipolymer is as the organic electroluminescence device of the material of luminescent layer, and its structure is as shown in Figure 2.
This device is followed successively by ITO/P1/LiF/Al; Promptly deposition one deck square resistance is that the tin indium oxide (ITO) of 10-20 Ω/mouth is as transparent anode on a glass substrate; On ITO, prepare one deck P1 material as luminescent layer through spin coating technique, vacuum evaporation LiF on this luminescent layer again is as impact plies; On impact plies, adopt vacuum coating technology metal refining Al 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-benzene 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 as electrode, also can adopt copper to make electrode, and P1 is spun to the SiO after octadecyl trichlorosilane (OTS) is modified as organic semiconductor layer 2On, contain 10 thereby make, the organic field effect tube of 20-two (9-octyl group carbazole) porphyrin-benzene multipolymer.
High, easy to utilize with above-mentioned polymer materials as the photoelectric transformation efficiency of polymer solar cell device, organic electroluminescent device and the organic field effect tube device of active material preparation.
The above embodiment has only expressed several kinds of embodiments 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 under the prerequisite that does not break away from the present invention's design, 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 accompanying claims.

Claims (10)

1. one kind contains carbazole porphyrin-benzene multipolymer, it is characterized in that, has following structural formula (III):
Figure FSA00000189030400011
Wherein, n is the integer between 1-100; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
2. preparation method who contains carbazole porphyrin-benzene multipolymer; It is characterized in that, be in oxygen-free environment, with 5; 15-two bromo-10; 20-alkyl carbazole porphyrin or derivatives thereof (I) and the Suzuki coupling reaction that two boric acid ester benzene (II) carry out under catalyzer and solvent existence condition obtain containing carbazole porphyrin-benzene multipolymer (III), and reaction formula is following:
Figure FSA00000189030400012
Wherein, n is the integer between 1-100; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
3. the preparation method who contains carbazole porphyrin-benzene multipolymer according to claim 2; It is characterized in that: said 5; 15-two bromo-10; 20-alkyl carbazole porphyrin (I) is 1: 1.5～1.5: 1 with the mol ratio of said pair of boric acid ester benzene (II), and temperature of reaction is 50-120 ℃, and the reaction times is 24～72 hours.
4. the preparation method who contains carbazole porphyrin-benzene multipolymer according to claim 2 is characterized in that: said catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand.
5. the preparation method who contains carbazole porphyrin-benzene multipolymer according to claim 4 is characterized in that: said organic palladium is Pd 2(dba) 3, Pd (OAc) 2, Pd (PPh 3) 4Or Pd (PPh 3) 2Cl 2In at least a; Said organophosphor ligand is tricyclohexyl phosphine or P (o-Tol) 3In at least a; The mol ratio of said organic palladium and said organophosphor ligand is 1: 2～1: 20.
6. according to claim 2 or the 4 or 5 described preparing methods that contain carbazole porphyrin-benzene multipolymer, it is characterized in that: the molar weight of said catalyzer be said pair of boric acid ester benzene (II) molar weight 0.05%～20%.
7. the preparation method who contains carbazole porphyrin-benzene multipolymer according to claim 2 is characterized in that: said solvent is at least a in benzene, toluene, glycol dimethyl ether, the THF.
8. organic solar batteries device; Comprise glass baseplate successively, be located at conductive layer on the said glass baseplate, be coated in and gather (3 on the said conductive layer; The 4-Ethylenedioxy Thiophene), gather (styrene sulfonic acid) layer, be coated in and saidly gather (3; The 4-Ethylenedioxy Thiophene), gather active coating on (styrene sulfonic acid) layer, be deposited on the metal Al layer on the said active coating and be used to encapsulate the epoxy resin of above-mentioned each layer; Said active coating comprises electron donor material and electron acceptor material, and said electron acceptor material is [6,6] phenyl-C 61-methyl-butyrate is characterized in that, said electron donor material contains carbazole porphyrin-benzene multipolymer for what have a structural formula (III):
Figure FSA00000189030400021
Wherein, n is the integer between 1-100; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
9. organic electroluminescence device; Comprise glass baseplate successively, be located at conductive layer on the said glass baseplate, be coated in luminescent layer on the said conductive layer, vapor deposition is at the LiF impact plies on the said luminescent layer and be deposited on the metal Al layer on the said LiF impact plies; It is characterized in that what the material of said luminescent layer had a structural formula (III) contains carbazole porphyrin-benzene multipolymer:
Figure FSA00000189030400031
Wherein, n is the integer between 1-100; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
10. organic field effect tube device comprises the doped silicon wafer base material successively, is located at the SiO of said doped silicon wafer substrate surface 2Insulation layer, be coated in said SiO 2The octadecyl trichlorosilane decorative layer on surface, be coated in the organic semiconductor layer on the said octadecyl trichlorosilane decorative layer and the source electrode and the drain electrode of organic semiconductor layer surface are set; It is characterized in that what the material of said organic semiconductor layer had a structural formula (III) contains carbazole porphyrin-benzene multipolymer:
Figure FSA00000189030400041
Wherein, n is the integer between 1-100; R 1And R 2Be hydrogen or C 1～C 32Alkyl.
CN 201010226125 2010-07-13 2010-07-13 Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof Expired - Fee Related CN102329417B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201010226125 CN102329417B (en) 2010-07-13 2010-07-13 Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201010226125 CN102329417B (en) 2010-07-13 2010-07-13 Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN102329417A true CN102329417A (en) 2012-01-25
CN102329417B CN102329417B (en) 2013-06-05

Family

ID=45481401

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201010226125 Expired - Fee Related CN102329417B (en) 2010-07-13 2010-07-13 Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN102329417B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138638A (en) * 2018-11-05 2020-05-12 湖北大学 Porphyrin-containing two-dimensional conjugated polymer and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1631890A (en) * 2004-12-10 2005-06-29 吉林大学 Tetraphenyl porphyrin derivative and its application in organic electroluminescent device
FR2892723A1 (en) * 2005-11-03 2007-05-04 Biomerieux Sa New electropolymerizable monomer, useful for detecting a target ligand in a biological sample, comprises an electropolymerizable unit e.g. acetylene and metallo-porphyrin substituted by ionized/ionizable entities

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1631890A (en) * 2004-12-10 2005-06-29 吉林大学 Tetraphenyl porphyrin derivative and its application in organic electroluminescent device
FR2892723A1 (en) * 2005-11-03 2007-05-04 Biomerieux Sa New electropolymerizable monomer, useful for detecting a target ligand in a biological sample, comprises an electropolymerizable unit e.g. acetylene and metallo-porphyrin substituted by ionized/ionizable entities

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138638A (en) * 2018-11-05 2020-05-12 湖北大学 Porphyrin-containing two-dimensional conjugated polymer and preparation method and application thereof
CN111138638B (en) * 2018-11-05 2022-06-21 湖北大学 Porphyrin-containing two-dimensional conjugated polymer and preparation method and application thereof

Also Published As

Publication number Publication date
CN102329417B (en) 2013-06-05

Similar Documents

Publication Publication Date Title
CN102906152B (en) Polymer containing units of fluorene, anthracene and benzothiadiazole, preparation method and uses thereof
CN102344549B (en) Porphyrin-pyrrolopyrrole copolymer containing carbazole, preparation method thereof and application thereof
CN102295754B (en) Naphthalene tetracarboxylic diimide-naphtho dithiophene-containing copolymer and preparation method as well as application thereof
CN102329415B (en) Porphyrin-quinoxaline copolymer containing carbazole, preparation method thereof and application thereof
CN102276804B (en) Perylene tetracarboxylic diimide copolymer containing dithiophen-pyrrole unit and preparation method and application thereof
CN102295756B (en) Carbazole porphyrin-thienothiadiazole copolymer as well as preparation method and application thereof
CN102453229B (en) Metalloporphyrin-thienopyrazine organic semiconductor material, preparation method thereof and application thereof
CN102329416B (en) Porphyrin-diazosulfide copolymer containing carbazole, preparation method and application thereof
CN102417584B (en) Metal porphyrin-anthracene organic semiconductor material as well as preparation method and application thereof
CN102344553A (en) Naphthalenetetracarboxylic acid diimide organic semiconductor material, preparation process thereof and application thereof
WO2011143806A1 (en) Porphyrin copolymer containing quinoxaline unit, preparation method and uses thereof
CN102329414B (en) Conjugated polymer containing cyclopentadienyl diene dithiophene-naphthalene tetracarboxylic diimide and preparation method and application thereof
CN102329417B (en) Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof
CN102268128B (en) Porphyrin copolymer containing thienophenazine unit as well as preparation method and application thereof
CN102453234B (en) Metalloporphyrin-thienothiadiazole organic semiconductor material and preparation method and application thereof
CN102295757B (en) Carbazolyl porphyrin-thienopyrazine-containing copolymer and preparation method as well as application thereof
CN102276800B (en) Triphenylamine unit porphyrin copolymer as well as preparation method and application thereof
CN102134307A (en) Perylene diimide-fluorene-thiophene and (3, 4-b) pyrazine conjugated polymer and preparation method and application thereof
CN103025737B (en) Silafluorene metalloporphyrin- benzene organic semiconductor material and preparing method and uses thereof
CN102295750B (en) Carbazole porphyrin-paranaphthalene copolymer and preparation method and application thereof
CN102417586B (en) Metal porphyrin-diazosulfide organic semiconductor material as well as preparation method and application thereof
CN102850527A (en) Copolymer of N,N'-disubstituted isoindigo and fluorene and preparation method and application thereof
CN102311538B (en) Copolymer material containing carbazole porphyrin-triphenylamine and preparation method and application thereof
CN102329413B (en) [2,1-b:3,4-b'] 2,2'-bithienyl-naphthalene diimide-containing conjugated polymer and preparation method and application thereof
CN102206330A (en) Bi-thiophene silole-containing conjugated polymer and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130605

Termination date: 20190713