CN103159921A - Thiophene pyrroledione based co-polymer material, and preparation method and application thereof - Google Patents

Thiophene pyrroledione based co-polymer material, and preparation method and application thereof Download PDF

Info

Publication number
CN103159921A
CN103159921A CN201110409569XA CN201110409569A CN103159921A CN 103159921 A CN103159921 A CN 103159921A CN 201110409569X A CN201110409569X A CN 201110409569XA CN 201110409569 A CN201110409569 A CN 201110409569A CN 103159921 A CN103159921 A CN 103159921A
Authority
CN
China
Prior art keywords
thienopyrroles
diketo
multipolymer
preparation
compd
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.)
Pending
Application number
CN201110409569XA
Other languages
Chinese (zh)
Inventor
周明杰
王平
张振华
黄辉
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
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 CN201110409569XA priority Critical patent/CN103159921A/en
Publication of CN103159921A publication Critical patent/CN103159921A/en
Pending legal-status Critical Current

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

Landscapes

  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention belongs to the field of solar cells, and discloses a thiophene pyrroledione based co-polymer material, and a preparation method and an application thereof. The co-polymer has the following structural formula (I). In the formula, both R1 and R2 represent a C1-C20 alkyl group and n is an integer ranging from 10 to 100. In the thiophene pyrroledione based co-polymer material provided by the invention, fluorene has easily modified photophysical properties, the solubility property and the photoelectric properties of the polymer can be adjusted by adjusting the length of alkyl chains of the fluorine; thiophene pyrroledione has a simple, symmetrical and polar structure and is beneficial to electron delocalization when the thiophene pyrroledione is polymerized with other monomers; and the thiophene pyrroledione also has relatively strong electron-withdrawing effect that results in reduction of an HOMO energy level and a LUMO energy level, thereby facilitating increasement of an open-circuit voltage. The performance can improve energy conversion efficiency of solar energy, so that the problem of low efficiency of polymer solar cells is solved.

Description

A kind of Thienopyrroles diketo multipolymer and its preparation method and application
Technical field
The present invention relates to the solar cell material field, relate in particular to a kind of Thienopyrroles diketo multipolymer and its preparation method and application.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.The silicon wafer battery that is used for ground at present is restricted its application because complex manufacturing, cost are high.In order to reduce the battery cost, expand range of application, people are seeking novel solar cell material always for a long time.Organic semiconductor material with its raw material be easy to get, cheap, preparation technology is simple, environmental stability good, have the good advantages such as photovoltaic effect to receive much concern.From N.S.Sariciftci in 1992 etc. at SCIENCE (N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C 60Between the Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed, but still much lower than the efficiency of conversion of inorganic solar cell.
Summary of the invention
The Thienopyrroles diketo multipolymer that provides a kind of effciency of energy transfer high is provided purpose one of the present invention.
A kind of Thienopyrroles diketo multipolymer with following structural formula (I):
Figure BDA0000118377870000011
In formula, R 1, R 2Be C 1～C 20Alkyl, n is 10～100 integer.
Another object of the present invention is to provide the preparation method of above-mentioned Thienopyrroles diketo multipolymer, comprise the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
A： B：
Figure BDA0000118377870000022
Wherein, in described compd A, R 1Be C 1～C 20Alkyl; In described compd B, R 2Be C 1～C 20Alkyl;
S2, under oxygen-free environment, with described compd A and compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer and alkaline solution, fully dissolving is rear after carrying out Suzuki coupling reaction 12～96h under 70～130 ℃, stop polyreaction after cooling, obtain the having following structural formula described Thienopyrroles diketo multipolymer of (I):
Figure BDA0000118377870000023
In formula, n is the integer of 10-100.
In the preparation method of above-mentioned Thienopyrroles diketo multipolymer, in described step S2:
Described catalyzer is organic palladium, and described organic palladium is selected from bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100; Perhaps
Described catalyzer also can for organic palladium (as, three dibenzalacetone two palladiums) and organophosphor ligand (as, tri-butyl phosphine) mixture, in this mixture, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8;
Described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF);
Described alkaline solution is selected from least a in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
Preferably, in the preparation method's of above-mentioned Thienopyrroles diketo multipolymer described step S2:
The preparation method of Thienopyrroles diketo multipolymer, described Suzuki coupling reaction temperature is 80～110 ℃; The described Suzuki coupling reaction time is 24～72h.
Another purpose of the present invention is to provide the application of above-mentioned Thienopyrroles diketo multipolymer in the organic solar batteries active coating.
Thienopyrroles diketo multipolymer provided by the invention has the photophysical property of easy modification, by regulating its alkyl chain length, thus solubility property and photoelectric properties that can telomerized polymer; The Thienopyrroles diketone has simply, symmetrical, polar structure, is conducive to electron delocalization after its and other monomer polymerization, and it also has stronger sucting electronic effect and causes HOMO and lumo energy reduction, is conducive to like this raising of open circuit voltage.This performance can improve the effciency of energy transfer of sun power, thereby solves the polymer solar battery low efficiency problem.
In addition, in the preparation method of above-mentioned isoindigo base co-polymer, adopted better simply synthetic route, thereby reduced technical process, material is cheap and easy to get, reduces manufacturing cost, and the material structure that makes is novel, and solubility property is good, and film forming properties is good.
Description of drawings
Fig. 1 is preparation technology's schema that the present invention contains Thienopyrroles diketo multipolymer;
Fig. 2 is the energy effect conversion efficiency curve figure of the multipolymer of embodiment 1 preparation;
Fig. 3 is the organic solar energy cell structure schematic diagram of embodiment 7.
Embodiment
Principle of design of the present invention: thiophene [3,4-c] and pyrroles-4, the 6-diketone causes vast organic solar batteries investigators' concern in recent years because of its higher effciency of energy transfer: the advantages such as simple, compact, symmetry and plane configuration, after it and other monomer copolymerization, this advantage will be conducive to electron delocalization; In addition, it also has stronger sucting electronic effect, is conducive to reduce HOMO and lumo energy; Simultaneously, the N-H bond energy enough easily modifies to improve solvability and photoelectric properties with functional groups such as other alkyl.
Thienopyrroles diketo multipolymer with following structural formula (I) provided by the invention:
Figure BDA0000118377870000041
In formula, R 1, R 2Be C 1～C 20Alkyl, n is 10～100 integer; N is preferably 50～70.
The preparation method of above-mentioned Thienopyrroles diketo multipolymer as shown in Figure 1, comprises the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
A：
Figure BDA0000118377870000042
2,7-hypoboric acid pinacol ester-9,9-dialkyl group fluorenes;
B：
Figure BDA0000118377870000043
N-alkyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone;
Wherein, in compd A, R 1Be C 1～C 20Alkyl; In compd B, R 2Be C 1～C 20Alkyl;
S2, oxygen-free environment (as, the oxygen-free environment that nitrogen, argon gas or nitrogen and argon gas gas mixture etc. consist of) under, with described compd A and compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer and alkaline solution, fully dissolving is rear after carrying out Suzuki coupling reaction 12～96h under 70～130 ℃, stop polyreaction after cooling, obtain mixed solution, comprise product in this mixed solution, namely have the described Thienopyrroles diketo multipolymer of following structural formula (I):
Figure BDA0000118377870000044
In formula, n is 10～100 integer;
S3, the product in step S2 is carried out purification process:
Add methyl alcohol in the mixed solution of step S2, carry out precipitating and process, filter with apparatus,Soxhlet's subsequently, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourlessly as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after 50 ℃ of dry 24h under vacuum, is obtained the Thienopyrroles diketo multipolymer of purifying.
In the preparation method of above-mentioned Thienopyrroles diketo multipolymer, in described step S2:
Described catalyzer is organic palladium, and described organic palladium is selected from bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100; Perhaps
Described catalyzer also can for organic palladium (as, three dibenzalacetone two palladiums) and organophosphor ligand (as, tri-butyl phosphine) mixture, in this mixture, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8;
Described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF);
Described alkaline solution is selected from least a in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
Preferably, in the preparation method's of above-mentioned Thienopyrroles diketo multipolymer described step S2:
Described Suzuki coupling reaction temperature is 80～110 ℃; The described Suzuki coupling reaction time is 24～72h.
Above-mentioned Thienopyrroles diketo multipolymer can be used as the organic solar batteries active layer material, is mainly the electron donor material in active coating.
In order to understand better the content of patent of the present invention, further illustrate technology case of the present invention below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, and wherein, the monomer of compd A is bought from the market and obtained, but monomer reference literature (the JACS J.Am.Chem.Soc. of compd B, 1997,119,5065.) disclosed method is synthetic or buy from the market and obtain.
Embodiment 1
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ 9,9-di-n-octyl-2,7-fluorenes-co-N-n-octyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R 1Be octane base, R 2Be the octane base, n is 60), its structural formula is as follows:
Figure BDA0000118377870000061
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118377870000062
With 2,7-hypoboric acid pinacol ester-9,9-dioctyl fluorene (193mg, 0.3mmol), N-octyl group-2,5-two bromo-thiophene [3,4-c] and pyrroles-4,6-diketone (126mg, 0.3mmol), tri-butyl phosphine (18mg, 0.09mmol) add in the flask that fills 12mL toluene, fully after the dissolving with solution of potassium carbonate (3mL, 2mol/L) join in flask, then logical nitrogen purge gas approximately after 30min, stir under 95 ℃, Suzuki coupling reaction 48h, stop polyreaction after cooling, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is under vacuum after 50 ℃ of dry 24h, be poly-{ 9,9-di-n-octyl-2,7-fluorenes-co-N-n-octyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 85%.
Test result is: Molecular weight (GPC, THF, R.I): M n=39.1kDa, M w/ M n=2.1.
Fig. 2 is the energy effect conversion efficiency curve figure of the multipolymer of embodiment 1 preparation; Result shows, at AM1.5; 100mW/cm 2Under illumination, the effciency of energy transfer that is the body heterojunction solar cell of donor material based on the polymkeric substance of embodiment 1 is 3.2%; AlIbrahim etc. have reported take Thienopyrroles diketo multipolymer as donor material, and PCBM is that acceptor material has prepared solar cell, and effciency of energy transfer is 2.5%.(Thin?Solid?Films，2006，673)
Embodiment 2
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ 9,9-dimethyl-2,7-fluorenes-co-N-eicosyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R 1Be methyl, R 2Be the NSC 62789 base, n is 40), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118377870000072
With 2,7-hypoboric acid pinacol ester-9,9-dimethyl fluorene (89mg, 0.2mmol) and N-NSC 62789 base-2,5-two bromo-thiophene [3,4-c] and pyrroles-4,6-diketone (118mg, 0.2mmol) add in the flask of the DMF solvent that fills 15ml, be dissolved into solution; And then with sodium carbonate solution (2mL, 2mol/L) join in flask, the evacuated flask deoxygenation also is filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol), stirring, Suzuki coupling reaction 24h, stop polyreaction after cooling under 120 ℃, obtains mixed solution.
Add 50mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is under vacuum after 50 ℃ of dry 24h, be poly-{ 9,9-dimethyl-2,7-fluorenes-co-N-NSC 62789 base-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate 79%.
Test result is: Molecular weight (GPC, THF, R.I): M n=25.3kDa, M w/ M n=2.2.
Embodiment 3
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ 9,9-two (NSC 62789 base)-2,7-fluorenes-co-N-methyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R 1Be NSC 62789 base, R 2Be methyl, n is 90), its structural formula is as follows:
Figure BDA0000118377870000081
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118377870000082
will, 2, 7-hypoboric acid pinacol ester-9, 9-two (NSC 62789 base) fluorenes (294mg, 0.3mmol) and N-methyl-2, 5-two bromo-thiophene [3, 4-c] and pyrroles-4, 6-diketone (98mg, 0.3mmol) add in the two-mouth bottle of the 50mL specification that fills the 15mL tetrahydrofuran (THF), be dissolved into solution, and then with sodium hydrogen carbonate solution (3mL, 2mol/L) join in solution, logical nitrogen and argon gas gas mixture, air-discharging is approximately after 20min, then with tetra-triphenylphosphine palladium (4mg, 0.003mmol) add in two-mouth bottle, fully lead to again nitrogen and argon gas gas mixture, continue air-discharging approximately after 10min, stir under 70 ℃, Suzuki coupling reaction 96h, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 9 after 50 ℃ of dry 24h under vacuum, 9-two (NSC 62789 base)-2,7-fluorenes-co-N-methyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 73%.
Test result is: Molecular weight (GPC, THF, R.I): M n=78.8kDa, M w/ M n=2.1.
Embodiment 4
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ 9,9-di-n-butyl-2,7-fluorenes-co-N-dodecyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R 1Be normal-butyl, R 2Be dodecyl, n is 100), its structural formula is as follows:
Figure BDA0000118377870000091
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118377870000092
With 2,7-hypoboric acid pinacol ester-9,9-di-n-butyl base fluorenes (89mg, 0.2mmol) and N-dodecyl-2,5-two bromo-thiophene [3,4-c] and pyrroles-4,6-diketone (95.8mg, 0.2mmol) add in the flask of the DMF solvent that fills 15ml, be dissolved into solution; And then with sodium carbonate solution (2mL, 2mol/L) join in flask, the evacuated flask deoxygenation also is filled with argon gas, then add bi triphenyl phosphine dichloride palladium (7.2mg, 0.01mmol), stirring, Suzuki coupling reaction 12h, stop polyreaction after cooling under 130 ℃, obtains mixed solution.
Add 50mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is under vacuum after 50 ℃ of dry 24h, be poly-{ 9,9-di-n-butyl-2,7-fluorenes-co-N-dodecyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate 86%.
Test result is: Molecular weight (GPC, THF, R.I): M n=59.6kDa, M w/ M n=2.1.
Embodiment 5
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ 9,9-two (n-tetradecane base)-2,7-fluorenes-co-N-n-decane base-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R 1Be n-tetradecane base, R 2Be the n-decane base, n is 10), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118377870000102
will, 2, 7-hypoboric acid pinacol ester-9, 9-two (n-tetradecane base) fluorenes (243mg, 0.3mmol) and N-decyl-2, 5-two bromo-thiophene [3, 4-c] and pyrroles-4, 6-diketone (135mg, 0.3mmol) add in the two-mouth bottle of the 50mL specification that fills the 15mL tetrahydrofuran (THF), be dissolved into solution, and then with sodium hydrogen carbonate solution (3mL, 2mol/L) join in solution, logical nitrogen and argon gas gas mixture, air-discharging is approximately after 20min, then with tetra-triphenylphosphine palladium (8mg, 0.006mmol) add in two-mouth bottle, fully lead to again nitrogen and argon gas gas mixture, continue air-discharging approximately after 10min, stir under 80 ℃, Suzuki coupling reaction 24h, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 9 after 50 ℃ of dry 24h under vacuum, 9-two (n-tetradecane base)-2,7-fluorenes-co-N-n-decane base-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 77%.
Test result is: Molecular weight (GPC, THF, R.I): M n=12.8kDa, M w/ M n=2.3.
Embodiment 6
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ N-normal hexane base-2,7-fluorenes-co-N-n-hexadecyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R 1Be normal hexane base, R 2Be n-hexadecyl, n is 30), its structural formula is as follows:
Figure BDA0000118377870000111
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118377870000112
with 2, 7-hypoboric acid pinacol ester-9-normal hexane base fluorenes (175.8mg, 0.3mmol), N-n-hexadecyl-2, 5-two bromo-thiophene [3, 4-c] and pyrroles-4, 6-diketone (160.6mg, 0.3mmol), three dibenzalacetone two palladium (13.75mg, 0.015mmol), tri-butyl phosphine (18mg, 0.09mmol) add in the flask that fills 12mL toluene, fully after the dissolving with solution of potassium carbonate (3mL, 2mol/L) join in flask, then logical nitrogen purge gas is approximately after 30min, stir under 110 ℃, Suzuki coupling reaction 72h, stop polyreaction after cooling, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is under vacuum after 50 ℃ of dry 24h, be poly-{ N-normal hexane base-2,7-fluorenes-co-N-n-hexadecyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 85%.
Test result is: Molecular weight (GPC, THF, R.I): M n=23.9kDa, M w/ M n=2.2.
Embodiment 7
The organic solar batteries of the present embodiment 7, its poly-{ 9,9-dioctyl-2,7-fluorenes-co-N-octyl group-thiophene [3,4-c] and pyrroles-4,6-diketone } that adopts that embodiment 1 makes is the electron donor material of active coating.
See also Fig. 3, this organic solar batteries comprises glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14 and the negative electrode 15 that stacks gradually.Transparent anode 12 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/; Middle supplementary layer 13 adopts poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material (referred to as PEDOT:PSS); Active coating 14 comprises electron donor material and electron acceptor material, and electron donor material adopts poly-{ 9,9-dioctyl-2,7-fluorenes-co-N-octyl group-thiophene [3,4-c] and pyrroles-4, the 6-diketone } of embodiment 1 preparation, and electron acceptor material can be [6,6] phenyl-C 61-methyl-butyrate (referred to as PCBM); Negative electrode 15 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 30nm, 130nm or 60nm.
Glass-base 11 can be used as bottom, during making, choose ito glass, and after ultrasonic cleaning, process supplementary layer 13 in the middle of applying with oxygen-Plasma on ito glass, in the middle of again the polymkeric substance of embodiment 1 preparation and electron acceptor material being coated on after by blend on supplementary layer 13, form active coating 14, and then by vacuum evaporation technology deposition cathode 15 on active coating 14, obtain above-mentioned solar cell device.This solar cell device also needs through heating 4h under 110 degrees centigrade of air tight conditions, drop to again room temperature, can effectively increase order and the regularity arranged between interior each group of molecule and molecule segment after device is annealed, improve transmission speed and the efficient of carrier mobility, and then improve photoelectric transformation efficiency.In the present embodiment, the thickness of negative electrode 15Al layer is respectively 170nm.
As shown in Figure 3, under illumination, light transmission glass-base 11 and ITO electrode 12, the conduction hole type electroluminescent material in active coating 14 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, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.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 16, can power to it.In this process, conduction hole type electroluminescent material can utilize luminous energy more fully because it has very wide spectral response range, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, is convenient to large batch of preparation.
Should be understood that, above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.

Claims (10)

1. Thienopyrroles diketo multipolymer with following structural formula (I):
Figure FDA0000118377860000011
In formula, R 1, R 2Be C 1～C 20Alkyl, n is 10～100 integer.
2. the preparation method of a Thienopyrroles diketo multipolymer, is characterized in that, comprises the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
A：
Figure FDA0000118377860000012
B：
Figure FDA0000118377860000013
Wherein, in described compd A, R 1Be C 1～C 20Alkyl; In described compd B, R 2Be C 1～C 20Alkyl;
S2, under oxygen-free environment, with described compd A and compd B according to the mol ratio add-on of 1: 1, add in the organic solvent that contains catalyzer and alkaline solution, fully dissolving is rear after carrying out Suzuki coupling reaction 12～96h under 70～130 ℃, stop polyreaction after cooling, obtain the having following structural formula described Thienopyrroles diketo multipolymer of (I):
Figure FDA0000118377860000014
In formula, n is 10～100 integer.
3. the preparation method of Thienopyrroles diketo multipolymer according to claim 2, is characterized in that, in described step S2, described catalyzer is organic palladium.
4. the preparation method of Thienopyrroles diketo multipolymer according to claim 3, is characterized in that, in described step S2, described organic palladium is selected from bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; The mol ratio of described organic palladium and described compd A is 1: 20～1: 100.
5. the preparation method of Thienopyrroles diketo multipolymer according to claim 2, is characterized in that, in described step S2, described catalyzer is the mixture of organic palladium and organophosphor ligand.
6. the preparation method of Thienopyrroles diketo multipolymer according to claim 5, it is characterized in that, in described mixture, described organic palladium is three dibenzalacetone two palladiums, described organophosphor ligand is the tri-butyl phosphine mixture, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8.
According to claim 3 to 6 arbitrary described Thienopyrroles diketo multipolymer the preparation method, it is characterized in that, in described step S2, described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
According to claim 3 to 6 arbitrary described Thienopyrroles diketo multipolymer the preparation method, it is characterized in that, in described step S2, described alkaline solution is selected from least a in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
According to claim 3 to 6 arbitrary described Thienopyrroles diketo multipolymer the preparation method, it is characterized in that, in described step S2, described Suzuki coupling reaction temperature is 80～110 ℃; The described Suzuki coupling reaction time is 24～72h.
10. the application of Thienopyrroles diketo multipolymer claimed in claim 1 in the organic solar batteries active coating.
CN201110409569XA 2011-12-09 2011-12-09 Thiophene pyrroledione based co-polymer material, and preparation method and application thereof Pending CN103159921A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110409569XA CN103159921A (en) 2011-12-09 2011-12-09 Thiophene pyrroledione based co-polymer material, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110409569XA CN103159921A (en) 2011-12-09 2011-12-09 Thiophene pyrroledione based co-polymer material, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN103159921A true CN103159921A (en) 2013-06-19

Family

ID=48583479

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110409569XA Pending CN103159921A (en) 2011-12-09 2011-12-09 Thiophene pyrroledione based co-polymer material, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN103159921A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100099840A1 (en) * 2007-04-13 2010-04-22 Jae-Min Moon Dioxypyrrolo-heteroaromatic compounds and organic electronic devices using the same
US20110114184A1 (en) * 2009-09-04 2011-05-19 Plextronics, Inc. Organic electronic devices and polymers, including photovoltaic cells and diketone-based and diketopyrrolopyrrole-based polymers
CN102201539A (en) * 2011-04-22 2011-09-28 华北电力大学 Polymer solar battery with inverted structure and fabrication method thereof
CN102344548A (en) * 2010-07-30 2012-02-08 海洋王照明科技股份有限公司 Copolymer containing fluorene and thiophene pyrroledione unit and preparation method and application of copolymer containing fluorene and thiophene pyrroledione unit

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100099840A1 (en) * 2007-04-13 2010-04-22 Jae-Min Moon Dioxypyrrolo-heteroaromatic compounds and organic electronic devices using the same
US20110114184A1 (en) * 2009-09-04 2011-05-19 Plextronics, Inc. Organic electronic devices and polymers, including photovoltaic cells and diketone-based and diketopyrrolopyrrole-based polymers
CN102344548A (en) * 2010-07-30 2012-02-08 海洋王照明科技股份有限公司 Copolymer containing fluorene and thiophene pyrroledione unit and preparation method and application of copolymer containing fluorene and thiophene pyrroledione unit
CN102201539A (en) * 2011-04-22 2011-09-28 华北电力大学 Polymer solar battery with inverted structure and fabrication method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANHUA HUANG ET AL.: "Synthesis and Light-Emtting Diodes Properties of Two New Fluorene Based Copolymers", 《ADVANCED MATERIALS RESEARCH》 *

Similar Documents

Publication Publication Date Title
CN103159925A (en) Isoindigo based co-polymer solar cell material, and preparation method and application thereof
CN103159926A (en) Isoindigo based co-polymer organic semiconductor material, and preparation method and application thereof
CN103159927A (en) Thiophene pyrroledione based co-polymer material, and preparation method and application thereof
CN104513370A (en) Diketopyrrolo pyrrole based copolymer, preparation method, and applications thereof
CN103665339A (en) Diketopyrrolopyrrole-base polymer, and preparation method and application thereof
CN104017187A (en) Isoindigo group-containing polymer as well as preparation method and application thereof
CN103159920B (en) Anthraquinonyl multipolymer solar cell material and its preparation method and application
CN103159915B (en) Isoindigo base co-polymer and its preparation method and application
CN103159928A (en) Thiophene pyrroledione based co-polymer material, and preparation method and application thereof
CN103159919B (en) Cyano group anthraquinonyl multipolymer solar cell material and its preparation method and application
CN103517935B (en) Phenyl-difluoride triazolyl solar cell material and its preparation method and application
CN103159923A (en) Isoindigo based co-polymer, and preparation method and application thereof
CN103159916A (en) Difluoro-benzotriazole based co-polymer organic semiconductor material, and preparation method and application thereof
CN103159917A (en) Thiophene pyrroledione based co-polymer organic semiconductor material, and preparation method and application thereof
CN103159921A (en) Thiophene pyrroledione based co-polymer material, and preparation method and application thereof
CN103159922A (en) Benzo-dithiophene based co-polymer solar cell material, and preparation method and application thereof
CN103012749A (en) Difluoro-benzo-triazole-based copolymer containing carbazole unit, preparation method thereof and application thereof
CN103130988A (en) Benzo bithiophene and bithiazole copolymer and preparing method thereof and solar cell comprising the same
CN104629003A (en) Isoindigo group containing polymer, preparation method and organic solar cell device
CN104558534A (en) Dithienyl benzotriazole side chain-containing polymer, preparation method thereof and organic solar cell device
CN104292432A (en) Polymer containing difluorobenzotriazole unit, and preparation method and application thereof
CN103534290B (en) Containing amine phenyl-difluoride and triazolyl polymkeric substance and its preparation method and application
CN104292429A (en) Anthraquinonyl-containing polymer, preparation method thereof and organic solar cell device
CN104513361A (en) Anthraquinone based copolymer, preparation method and applications thereof
CN103804644A (en) Benzothiazolyl copolymer as well as 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
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130619