CN103159922A - Benzo-dithiophene based co-polymer solar cell material, and preparation method and application thereof - Google Patents

Benzo-dithiophene based co-polymer solar cell material, and preparation method and application thereof Download PDF

Info

Publication number
CN103159922A
CN103159922A CN2011104097708A CN201110409770A CN103159922A CN 103159922 A CN103159922 A CN 103159922A CN 2011104097708 A CN2011104097708 A CN 2011104097708A CN 201110409770 A CN201110409770 A CN 201110409770A CN 103159922 A CN103159922 A CN 103159922A
Authority
CN
China
Prior art keywords
solar cell
benzo
cell material
preparation
multipolymer
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
CN2011104097708A
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 CN2011104097708A priority Critical patent/CN103159922A/en
Publication of CN103159922A publication Critical patent/CN103159922A/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 benzo-dithiophene based co-polymer solar cell 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 benzo-dithiophene based co-polymer solar cell material provided by the invention, benzo-dithiophene has easily modified photophysical properties; the co-polymer of the benzo-dithiophene presents excellent photovoltaic performance; bithiazole is an excellent electron acceptor and can narrow a band gap of the polymer after two thiophenes are connected on the bithiazole; and the performance can improve energy conversion efficiency of solar energy, so that the problem of low efficiency of polymer solar cells is solved.

Description

Benzo dithienyl multipolymer solar cell material 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 benzo dithienyl multipolymer solar cell material 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.The main restricting factor that limiting performance improves has: the spectral response of organic semiconductor material and solar radiation spectrum do not mate, the electrode collection effciency of the carrier mobility that organic semiconductor is relatively low and lower current carrier etc.In order to make polymer solar battery obtain actual application, the material of development of new increases substantially the top priority that its effciency of energy transfer is still this research field.
Over the past two years, the basic conjugated polymers of benzo two thiophene (BDT) had demonstrated good photovoltaic performance.The people such as Yang have synthesized the conjugated polymers of a series of BDT bases, and these polymkeric substance have extraordinary photoelectric properties, and the highest effciency of energy transfer is 7% for (PCE).Recently, the Leclerc group has also been reported a kind of new conjugated polymers that contains the BDT base (PBDTTPD), when the active coating area is 1cm 2The time, PCE is up to 5.5%.In order to design and to synthesize the polymkeric substance with appropriate bandgap and molecular entergy level, new electron acceptor material plays a part crucial in the new D-A structural polymer of exploitation.Research finds that thiazole is a typical electron deficiency unit, and it comprises an electrophilic imine group, contains benzothiazolyl in copolymer chain and shows higher hole mobility, and each unit increases the band gap that two thienyls can reduce multipolymer.Therefore benzo two thiophene and two thiophene-thiazoles and thiazole copolymer material are a kind of very promising high performance solar cells materials.
Summary of the invention
The benzo dithienyl multipolymer solar cell material that provides a kind of effciency of energy transfer high is provided purpose one of the present invention.
A kind of benzo dithienyl multipolymer solar cell material with following structural formula (I):
Figure BDA0000118375820000021
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 benzo dithienyl multipolymer solar cell material, comprise the steps:
Under oxygen-free environment, with structural formula be
Figure BDA0000118375820000022
Compd A and structural formula be
Figure BDA0000118375820000023
Compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer, fully after the dissolving after carrying out Stille coupling reaction 6～60h under 70～130 ℃, obtain having following structural formula after the cooling stopped reaction described benzo dithienyl multipolymer solar cell material of (I):
Figure BDA0000118375820000024
Above-mentioned various in, R 1Be C 1～C 20Alkyl, R 2Be C 1～C 20Alkyl, n is 10～100 integer.
In the preparation method of above-mentioned benzo dithienyl multipolymer solar cell material:
Described catalyzer is organic palladium, and this 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 be organic palladium (as, three dibenzalacetone two palladiums) and the organophosphor ligand mixture of (as, tri-butyl phosphine); The mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and in described mixture, 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).
In the preparation method of above-mentioned benzo dithienyl multipolymer solar cell material, preferably, described Stille coupling reaction temperature is 80～110 ℃; The described Stille coupling reaction time is 12～48h.
Another purpose of the present invention is to provide the application of above-mentioned benzo dithienyl multipolymer solar cell material in organic solar batteries.
Benzo dithienyl multipolymer solar cell material provided by the invention, benzo two thiophene have the photophysical property of easy modification, and its co-polymer has demonstrated good photovoltaic performance; And thiazole is after a fine electron acceptor(EA) links two thiophene, to be that the band gap of polymkeric substance narrows down.This performance can improve the effciency of energy transfer of sun power, thereby solves the polymer solar battery low efficiency problem.
Separately, in the preparation method of above-mentioned Thienopyrroles diketo multipolymer, it has adopted better simply synthetic route, thereby the minimizing technical process, starting material are cheap and easy to get, reduce manufacturing cost, the polymeric material novel structure that makes, solubility property is good, and film forming properties is good, and this copolymer material is applicable to solar cell device.
Description of drawings
Fig. 1 is preparation technology's schema of benzo dithienyl multipolymer solar cell material of the present invention;
Fig. 2 is the effciency of energy transfer graphic representation of the solar cell material of embodiment 1;
Fig. 3 is the structural representation of the solar cell of embodiment 7.
Embodiment
Benzo dithienyl multipolymer solar cell material with following structural formula (I) provided by the invention:
Figure BDA0000118375820000041
In formula, R 1, R 2Be C 1～C 20Alkyl, n is 10～100 integer; Preferred n is 40～70
The preparation method of above-mentioned benzo dithienyl multipolymer solar cell material 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 BDA0000118375820000042
2,5-two (5-bromo-3-alkyl-2-thiophene) thiazole is [5,4-d] thiazole also
B：
Figure BDA0000118375820000043
2,6-, two tin trimethyls-4,8-two (alkoxyl group)-benzo two thiophene
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, fully dissolving is rear after carrying out Stille coupling reaction 6～60h under 70～130 ℃, the cooling stopped reaction obtains mixed solution, comprises product in this mixed solution, namely has the described benzo dithienyl multipolymer solar cell material of following structural formula (I):
Figure BDA0000118375820000051
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, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after 50 ℃ of dry 24h under vacuum, is obtained the benzo dithienyl multipolymer solar cell material of tool purifying:
In the preparation method of above-mentioned benzo dithienyl multipolymer solar cell material, in described step S2:
Described catalyzer is organic palladium, and this 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) with organophosphor ligand (as, tri-butyl phosphine) mixture, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and in described mixture, 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).
The preparation method of benzo dithienyl multipolymer solar cell material, in described step S2, preferably:
Described Stille coupling reaction temperature is 80～110 ℃; The described Stille coupling reaction time is 12～48h.
Above-mentioned benzo dithienyl multipolymer solar cell material can be applied in the active coating of organic solar batteries.
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, wherein, but the monomer reference literature (Adv.Mater. of compd A, 2007,19,4160.) disclosed method is synthetic or buy from the market and obtain, but monomer reference literature (Macromolecules, 2008 of compd B, 41,6012.) disclosed method is synthetic or buy from the market and obtain.
Embodiment 1
The benzo dithienyl multipolymer solar cell material of the present embodiment, i.e. poly-{ 2,5-two (3-n-octyl-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, 8-two (n-octyloxy)-benzo two thiophene }, wherein, R 1Be octane base, R 2Be the octane base, n is 60, and its structural formula is as follows:
Figure BDA0000118375820000061
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118375820000062
with 2,5-two (5-bromo-3-n-octyl-2-thiophene) thiazole also [5,4-d] thiazole (257mg, 0.3mmol) and 2,6-two tin trimethyls-4,8-two (n-octyloxy)-benzo two thiophene (231mg, 0.3mmol), three dibenzalacetone two palladium (13.75mg, 0.015mmol) and tri-butyl phosphine (24.2mg, 0.12mmol) add in the flask that fills 12mL toluene, be dissolved into solution, fully logical nitrogen purge gas is approximately after 30min in the flask, stir under 95 ℃, Stille coupling reaction 40h, 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, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 2 after 50 ℃ of dry 24h under vacuum, 5-two (3-n-octyl-2-thiophene) thiazole also [5,4-d] thiazole-co-4,8-two (n-octyloxy)-benzo two thiophene } product, productive rate is 74%.
Test result is: Molecular weight (GPC, THF, R.I): M n=58.8kDa, M w/ M n=2.2.
Fig. 2 is the effciency of energy transfer graphic representation of the solar cell material of embodiment 1; 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 4.1%; Miao etc. have reported that take two thieno-thiazolyl multipolymers as donor material, PCBM is that acceptor material has prepared solar cell, and effciency of energy transfer is 2.1%.(Adv.Mater.2009，27，3831)
Embodiment 2
The benzo dithienyl multipolymer solar cell material of the present embodiment, i.e. poly-{ 2,5-two (3-methyl-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, 8-two (NSC 62789 oxygen base)-benzo two thiophene }, wherein, R 1Be methyl, R 2Be the NSC 62789 base, n is 40, and its structural formula is as follows:
Figure BDA0000118375820000071
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118375820000072
With 2,5-two (5-bromo-3-methyl-2-thiophene) thiazole also [5,4-d] thiazole (132mg, 0.2mmol) and 2,6-two tin trimethyls-4,8-two (eicosane oxygen base)-benzo two thiophene (222mg, 0.2mmol) add in the DMF flask that fills 15ml, be dissolved into solution, the evacuated flask deoxygenation also is filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol), stirring, Stille coupling reaction 12h under 120 ℃, stop polyreaction after cooling, obtain mixed solution.
Add 50mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 2 after 50 ℃ of dry 24h under vacuum, 5-two (3-methyl-2-thiophene) thiazole also [5,4-d] thiazole-co-4,8-two (NSC 62789 oxygen base)-benzo two thiophene } product, productive rate 65%.
Test result is: Molecular weight (GPC, THF, R.I): M n=46.9kDa, M w/ M n=2.3.
Embodiment 3
The benzo dithienyl multipolymer solar cell material of the present embodiment, i.e. poly-{ 2,5-two (3-NSC 62789 base-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, 8-dimethoxy-benzo two thiophene }, wherein, R 1Be NSC 62789 base, R 2Be methyl, n is 80, and its structural formula is as follows:
Figure BDA0000118375820000081
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118375820000091
with 2, 5-two (5-bromo-3-eicosyl-2-thiophene) thiazole also [5, 4-d] thiazole (358mg, 0.3mmol) and 2, 6-two tin trimethyls-4, 8-two (methoxyl group)-benzo two thiophene (173mg, 0.3mmol) add in the two-mouth bottle of the 50mL specification that fills the 15mL tetrahydrofuran (THF), be dissolved into solution, fully lead to nitrogen and argon gas gas mixture in two-mouth bottle, air-discharging is approximately after 20min, then with tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, fully logical nitrogen and argon gas gas mixture air-discharging are approximately after 10min again, stir under 80 ℃, Stille coupling reaction 48h, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 2 after 50 ℃ of dry 24h under vacuum, 5-two (3-NSC 62789 base-2-thiophene) thiazole also [5,4-d] thiazole-co-4,8-dimethoxy-benzo two thiophene } product, productive rate is 82%.
Test result is: Molecular weight (GPC, THF, R.I): M n=66.7kDa, M w/ M n=2.1.
Embodiment 4
The benzo dithienyl multipolymer solar cell material of the present embodiment, i.e. poly-{ 2,5-two (3-normal butane base-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, 8-two (n-hexadecane oxygen base)-benzo two thiophene }, wherein, R 1Be normal butane base, R 2Be n-hexadecyl, n is 100, and its structural formula is as follows:
Figure BDA0000118375820000101
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118375820000102
With 2,5-two (5-bromo-3-normal butane base-2-thiophene) thiazole also [5,4-d] thiazole (149mg, 0.2mmol) and 2,6-two tin trimethyls-4,8-two (n-hexadecane oxygen base)-benzo two thiophene (199mg, 0.2mmol) add in the tetrahydrofuran (THF) flask that fills 15ml, be dissolved into solution, the evacuated flask deoxygenation also is filled with argon gas, then adds bi triphenyl phosphine dichloride palladium (7.2mg, 0.001mmol), stirring, Stille coupling reaction 60h, stop polyreaction after cooling under 70 ℃, obtains mixed solution.
Add 50mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 2 after 50 ℃ of dry 24h under vacuum, 5-two (3-normal butane base-2-thiophene) thiazole also [5,4-d] thiazole-co-4,8-two (n-hexadecane oxygen base)-benzo two thiophene } product, productive rate 87%.
Test result is: Molecular weight (GPC, THF, R.I): M n=108.5kDa, M w/ M n=2.0.
Embodiment 5
The benzo dithienyl multipolymer solar cell material of the present embodiment, i.e. poly-{ 2,5-two (3-n-hexadecyl-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, 8-two normal hexane oxygen base-benzo two thiophene }, wherein, R 1Be n-hexadecyl, R 2Be the normal hexane base, n is 10, and its structural formula is as follows:
Figure BDA0000118375820000111
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118375820000112
with 2, 5-two (5-bromo-3-n-hexadecyl-2-thiophene) thiazole also [5, 4-d] thiazole (324mg, 0.3mmol) and 2, 6-two tin trimethyls-4, 8-two (normal hexane oxygen base)-benzo two thiophene (215mg, 0.3mmol) add and fill 15mLN, in the two-mouth bottle of the 50mL specification of dinethylformamide, be dissolved into solution, fully lead to nitrogen and argon gas gas mixture in two-mouth bottle, air-discharging is approximately after 20min, then with tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, fully logical nitrogen and argon gas gas mixture air-discharging are approximately after 10min again, stir under 130 ℃, Stille coupling reaction 6h, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 2 after 50 ℃ of dry 24h under vacuum, 5-two (3-n-hexadecyl-2-thiophene) thiazole also [5,4-d] thiazole-co-4,8-two normal hexane oxygen base-benzo two thiophene } product, productive rate is 59%.
Test result is: Molecular weight (GPC, THF, R.I): M n=12.8kDa, M w/ M n=2.4.
Embodiment 6
The benzo dithienyl multipolymer solar cell material of the present embodiment, i.e. poly-{ 2,5-two (3-n-octyl-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, 8-two (n-tetradecane oxygen base)-benzo two thiophene }, wherein, R 1Be octane base, R 2Be the n-tetradecane base, n is 30, and its structural formula is as follows:
Figure BDA0000118375820000121
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000118375820000122
with 2,5-two (5-bromo-3-n-octyl-2-thiophene) thiazole also [5,4-d] thiazole (257mg, 0.3mmol) and 2,6-two tin trimethyls-4,8-two (n-tetradecane oxygen base)-benzo two thiophene (282mg, 0.3mmol), three dibenzalacetone two palladium (13.75mg, 0.015mmol) and tri-butyl phosphine (12.1mg, 0.06mmol) add in the flask that fills 12mL toluene, be dissolved into solution, fully logical nitrogen purge gas is approximately after 30min in the flask, stir under 110 ℃, Stille coupling reaction 12h, 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, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 2 after 50 ℃ of dry 24h under vacuum, 5-two (3-n-octyl-2-thiophene) thiazole also [5,4-d] thiazole-co-4,8-two (n-tetradecane oxygen base)-benzo two thiophene } product, productive rate is 66%.
Test result is: Molecular weight (GPC, THF, R.I): M n=34.3kDa, M w/ M n=2.3.
Embodiment 7
The organic solar batteries of the present embodiment 7, its poly-{ 2,5-two (3-octyl group-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, 8-two (octyloxy)-benzo two thiophene } 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, electron donor material adopts poly-{ 2 of embodiment 1 preparation, 5-two (3-octyl group-2-thiophene) thiazole also [5,4-d] thiazole-co-4,8-two (octyloxy)-benzo two thiophene }, electron acceptor material can be [6,6] phenyl-C61-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 160nm, 30nm, 120nm or 50nm.
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 160nm.
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. benzo dithienyl multipolymer solar cell material with following structural formula (I):
In formula, R 1, R 2Be C 1～C 20Alkyl, n is 10～100 integer.
2. the preparation method of a benzo dithienyl multipolymer solar cell material, is characterized in that, comprises the steps:
Under oxygen-free environment, with structural formula be
Figure FDA0000118375810000012
Compd A and structural formula be Compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer, fully dissolving is rear after carrying out Stille coupling reaction 6～60h under 70～130 ℃, the cooling stopped reaction, obtain the having following structural formula described benzo dithienyl multipolymer solar cell material of (I):
Figure FDA0000118375810000014
Above-mentioned various in, R 1Be C 1～C 20Alkyl, R 2Be C 1～C 20Alkyl, n is 10～100 integer.
3. the preparation method of benzo dithienyl multipolymer solar cell material according to claim 2, is characterized in that, described catalyzer is organic palladium.
4. the preparation method of benzo dithienyl multipolymer solar cell material according to claim 3, is characterized in that, 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 benzo dithienyl multipolymer solar cell material according to claim 2, is characterized in that, described catalyzer is the mixture of organic palladium and organophosphor ligand.
6. the preparation method of benzo dithienyl multipolymer solar cell material according to claim 5, is characterized in that, described organic palladium is three dibenzalacetone two palladiums, and described organophosphor ligand is tri-butyl phosphine.
7. the preparation method of benzo dithienyl multipolymer solar cell material according to claim 5, it is characterized in that, 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 7 arbitrary described benzo dithienyl multipolymer solar cell material the preparation method, it is characterized in that, described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
According to claim 3 to 7 arbitrary described benzo dithienyl multipolymer solar cell material the preparation method, it is characterized in that, described Stille coupling reaction temperature is 80～110 ℃, the described Stille coupling reaction time is 12～48h.
10. the application of benzo dithienyl multipolymer solar cell material claimed in claim 1 in organic solar batteries.
CN2011104097708A 2011-12-09 2011-12-09 Benzo-dithiophene based co-polymer solar cell material, and preparation method and application thereof Pending CN103159922A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011104097708A CN103159922A (en) 2011-12-09 2011-12-09 Benzo-dithiophene based co-polymer solar cell material, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011104097708A CN103159922A (en) 2011-12-09 2011-12-09 Benzo-dithiophene based co-polymer solar cell material, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN103159922A true CN103159922A (en) 2013-06-19

Family

ID=48583480

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011104097708A Pending CN103159922A (en) 2011-12-09 2011-12-09 Benzo-dithiophene based co-polymer solar cell material, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN103159922A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111019095A (en) * 2019-10-23 2020-04-17 苏州大学 Ternary random conjugated polymer based on 2, 5-di (2-thienyl) thiazolo [5,4-d ] thiazolyl

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011051292A1 (en) * 2009-10-28 2011-05-05 University Of Washington Copolymer semiconductors comprising thiazolothiazole or benzobisthiazole, or benzobisoxazole electron acceptor subunits, and electron donor subunits, and their uses in transistors and solar cells
WO2011085004A2 (en) * 2010-01-05 2011-07-14 Konarka Technologies, Inc. Photovoltaic cell with benzodithiophene-containing polymer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011051292A1 (en) * 2009-10-28 2011-05-05 University Of Washington Copolymer semiconductors comprising thiazolothiazole or benzobisthiazole, or benzobisoxazole electron acceptor subunits, and electron donor subunits, and their uses in transistors and solar cells
WO2011085004A2 (en) * 2010-01-05 2011-07-14 Konarka Technologies, Inc. Photovoltaic cell with benzodithiophene-containing polymer

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LEE S K ET AL: "Synthesis and characterization of thiazolothiazole-based polymers and their applications in polymer solar cells", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 *
SHI Q Q ET AL: "Synthesis of Copolymers Based on Thiazolothiazole and Their Applications in Polymer Solar Cells", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 *
YANG M ET AL: "Synthesis and photovoltaic properties of copolymers from Benzodithiophene and Thiazole", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111019095A (en) * 2019-10-23 2020-04-17 苏州大学 Ternary random conjugated polymer based on 2, 5-di (2-thienyl) thiazolo [5,4-d ] thiazolyl

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
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
CN103159919B (en) Cyano group anthraquinonyl multipolymer solar cell material and its preparation method and application
CN104513367A (en) Quinoxaline based copolymer, preparation method and applications thereof
CN103665339A (en) Diketopyrrolopyrrole-base polymer, and preparation method and application thereof
CN104513370A (en) Diketopyrrolo pyrrole based copolymer, preparation method, and applications thereof
CN103159923A (en) Isoindigo based co-polymer, and preparation method and application thereof
CN103517935B (en) Phenyl-difluoride triazolyl solar cell material and its preparation method and application
CN103159928A (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
CN103159916A (en) Difluoro-benzotriazole based co-polymer organic semiconductor material, and preparation method and application thereof
CN104592497A (en) Dithienylethylene-based copolymer solar battery material, and preparation method and application thereof
CN104558537A (en) Triphenylamine side chain-containing polymer, preparation method thereof and organic solar cell device
CN104177600A (en) Polymer containing dithiazolebenzothiadiazole group, preparation method and organic solar cell device thereof
CN103159917A (en) Thiophene pyrroledione based co-polymer organic semiconductor material, and preparation method and application thereof
CN103130988A (en) Benzo bithiophene and bithiazole copolymer and preparing method thereof and solar cell comprising the same
CN103665338A (en) Diketopyrrolopyrrole-base polymer, and preparation method and application thereof
CN104558534A (en) Dithienyl benzotriazole side chain-containing polymer, preparation method thereof and organic solar cell device
CN104558535A (en) Dithienyl benzotriazole side chain-containing polymer, preparation method thereof and organic solar cell device
CN103159918A (en) Anthraquinone dithiophene based co-polymer solar cell material, and a preparation method and an application thereof
CN103804644A (en) Benzothiazolyl copolymer as well as preparation method and application thereof
CN104250365A (en) Anthraquinonyl group-containing polymer, preparation method thereof, and organic solar cell device

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