CN103804650A - Difluorobenzothiadiazole-based copolymer and preparation method and application thereof - Google Patents
Difluorobenzothiadiazole-based copolymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN103804650A CN103804650A CN201210450648.XA CN201210450648A CN103804650A CN 103804650 A CN103804650 A CN 103804650A CN 201210450648 A CN201210450648 A CN 201210450648A CN 103804650 A CN103804650 A CN 103804650A
- Authority
- CN
- China
- Prior art keywords
- phenyl
- difluoride
- thiadiazolyl group
- palladium
- preparation
- 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
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
- Photovoltaic Devices (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention provides a difluorobenzothiadiazole-based copolymer and a preparation method and application thereof. The structural formula of the difluorobenzothiadiazole-based copolymer is shown in the specification, wherein R is selected from alkyl having 1-20 carbon atoms, and n is an integer ranging from 10 to 100. Dithiophene is introduced to reduce the band gap of the difluorobenzothiadiazole-based copolymer, so that the absorption spectrum is widened, cyclopentane[2,1-b:3,4-b']dithiophthene in the difluorobenzothiadiazole-based copolymer has easily modified photophysical property, and the difluorobenzothiadiazole-based copolymer shows excellent photovoltaic performance. By using the difluorobenzothiadiazole-based copolymer in a solar cell, the energy conversion efficiency of an organic solar cell device can be increased.
Description
Technical field
The present invention relates to solar cell material field, particularly relate to a kind of phenyl-difluoride thiadiazolyl group multipolymer and its preparation method and application.
Background technology
Utilize cheap material to prepare low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.The current silicon wafer battery for ground, because complex manufacturing, cost are high, is restricted its application.In order to reduce battery cost, expand range of application, people are finding 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 advantages such as good photovoltaic effect to receive much concern.On SCIENCE, report conjugated polymers and C from N.S.Sariciftci in 1992 etc.
60between 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 is not mated with solar radiation spectrum, the electrode collection effciency of the carrier mobility that organic semiconductor is relatively low and lower current carrier etc.For polymer solar battery is on the actual application, the material of development of new, and then increase substantially its effciency of energy transfer and be still the top priority of this research field.
Summary of the invention
Based on this, be necessary to provide the good phenyl-difluoride of a kind of photovoltaic performance thiadiazolyl group multipolymer and preparation method thereof.
A kind of phenyl-difluoride thiadiazolyl group multipolymer, have following structural formula:
Wherein, R is selected from C
1~ C
20alkyl, the integer that n is 10 ~ 100.
A preparation method for phenyl-difluoride thiadiazolyl group multipolymer, comprises the following steps:
Raw material A and raw material B as follows is provided respectively:
Under the atmosphere of shielding gas; after the raw material A that is 1:1 ~ 1.2 by mol ratio and raw material B, catalyzer and organic solvent mix; at 70 ℃ ~ 130 ℃, react 6h ~ 60h, after separating-purifying, must there is phenyl-difluoride the thiadiazolyl group multipolymer of following structural formula:
Wherein, the integer that n is 10 ~ 100.
In an embodiment, described shielding gas is the gas mixture of argon gas, nitrogen or nitrogen and argon gas therein.
In an embodiment, the mol ratio of described catalyzer and described raw material A is 1:20 ~ 1:100 therein; Described catalyzer is the mixture of organic palladium or organic palladium and organophosphorus ligand; Described organic palladium is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, the mixture of described organic palladium and organophosphorus ligand is mixture or three or two argon benzyl acetone two palladiums and the 2-dicyclohexyl phosphine-2 ' of palladium and three (o-methoxyphenyl) phosphine, the mixture of 6 '-dimethoxy-biphenyl; In the mixture of described organic palladium and organophosphorus ligand, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 8.
In an embodiment, described organic solvent is at least one in toluene, DMF and tetrahydrofuran (THF) therein.
In an embodiment, temperature of reaction is 90 ℃ ~ 120 ℃ therein, and the reaction times is 12h ~ 48h.
Therein in an embodiment, after described separating-purifying comprises the steps: that reaction finishes, reacted solution is cooled to room temperature, add methyl alcohol precipitating, filter, gained precipitation adopts soxhlet extraction to use successively methyl alcohol and normal hexane extracting, is precipitated to colourless with chloroform extracting afterwards, collect chloroformic solution and be spin-dried for and obtain red powder, described red powder is dry under vacuum.
A kind of organic solar batteries device, comprises the substrate, anode, buffer layer, active coating and the negative electrode that stack gradually, and described active coating comprises phenyl-difluoride the thiadiazolyl group multipolymer with following structural formula:
Wherein, R is selected from C
1~ C
20alkyl, the integer that n is 10 ~ 100.
In an embodiment, the material of described buffer layer is the mixture of poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid therein.
In an embodiment, described negative electrode adopts aluminium electrode or double-metal layer electrode therein.
Above-mentioned phenyl-difluoride thiadiazolyl group multipolymer, reduce the band gap of phenyl-difluoride thiadiazolyl group multipolymer by introducing two thiophene, thereby widen absorption spectrum, pentamethylene [2 in phenyl-difluoride thiadiazolyl group multipolymer, 1-b:3,4-b '] 1,4-Dithiapentalene has the photophysical property of easy modification, and phenyl-difluoride thiadiazolyl group multipolymer demonstrate good photovoltaic performance.
The preparation method of above-mentioned phenyl-difluoride thiadiazolyl group multipolymer, adopts better simply synthetic route, has reduced technical process, and meanwhile, raw material is cheap and easy to get, has reduced manufacturing cost.
In addition, above-mentioned phenyl-difluoride thiadiazolyl group copolymer structure novelty, solubility property is good, and film forming properties is good, applicable to organic solar batteries device.
Accompanying drawing explanation
Fig. 1 is the phenyl-difluoride of an embodiment the preparation method's of thiadiazolyl group multipolymer schema;
Fig. 2 is the structure iron of the organic solar batteries device of an embodiment;
Fig. 3 is the phenyl-difluoride of embodiment 1 the ultraviolet-visible absorption spectroscopy figure of thiadiazolyl group multipolymer.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
The phenyl-difluoride of one embodiment thiadiazolyl group multipolymer, have following structural formula:
Wherein, R is selected from C
1~ C
20alkyl, the integer that n is 10 ~ 100.
Above-mentioned phenyl-difluoride thiadiazolyl group multipolymer, reduce the band gap of phenyl-difluoride thiadiazolyl group multipolymer by introducing two thiophene, thereby widen absorption spectrum, pentamethylene [2 in phenyl-difluoride thiadiazolyl group multipolymer, 1-b:3,4-b '] 1,4-Dithiapentalene has the photophysical property of easy modification, and phenyl-difluoride thiadiazolyl group multipolymer demonstrate good photovoltaic performance.
Refer to Fig. 1, the preparation method of the phenyl-difluoride of an embodiment thiadiazolyl group multipolymer, comprises the following steps:
Step S10, provide raw material A and raw material B as follows respectively:
Raw material A and raw material B are the product that lark prestige scientific & technical corporation produces.
Step S20, under the atmosphere of shielding gas; after the raw material A that is 1:1 ~ 1.2 by mol ratio and raw material B, catalyzer and organic solvent mix; at 70 ℃ ~ 130 ℃, react 6h ~ 60h, after separating-purifying, must there is phenyl-difluoride the thiadiazolyl group multipolymer of following structural formula:
Wherein, the integer that n is 10 ~ 100.
Wherein, temperature of reaction is preferably 90 ℃ ~ 120 ℃, and the reaction times is preferably 12h ~ 48h.
Shielding gas is the gas mixture of argon gas, nitrogen or nitrogen and argon gas.
Organic solvent can be at least one in toluene, DMF and tetrahydrofuran (THF).
The mol ratio of catalyzer and raw material A is 1:20 ~ 1: 100; Catalyzer is the mixture of organic palladium or organic palladium and organophosphorus ligand; Organic palladium is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, the mixture of organic palladium and organophosphorus ligand is mixture or three or two argon benzyl acetone two palladiums and the 2-dicyclohexyl phosphine-2 ' of palladium and three (o-methoxyphenyl) phosphine, the mixture of 6 '-dimethoxy-biphenyl; In the mixture of organic palladium and organophosphorus ligand, the mol ratio of organic palladium and organophosphorus ligand is 1:4 ~ 8.
Preferably, after separating-purifying comprises the steps: that reaction finishes, reacted solution is cooled to room temperature, add methyl alcohol precipitating, filter, gained precipitation adopts soxhlet extraction to use successively methyl alcohol and normal hexane extracting, is precipitated to colourless with chloroform extracting afterwards, collect chloroformic solution and be spin-dried for and obtain red powder, red powder is dry under vacuum.Concrete, by red powder 50 ℃ of dry 24h under vacuum.
The preparation method of above-mentioned phenyl-difluoride thiadiazolyl group multipolymer, adopts better simply synthetic route, has reduced technical process, and meanwhile, raw material is cheap and easy to get, has reduced manufacturing cost.
Above-mentioned phenyl-difluoride thiadiazolyl group copolymer structure novelty, solubility property is good, and film forming properties is good, is a kind of electron donor(ED) unit efficiently in D-A type Polymer photovoltaic materials, can be applied in solar cell, improve the effciency of energy transfer of organic solar batteries device.
Refer to Fig. 2, the organic solar batteries device 100 of an embodiment, comprises the substrate 110, anode 120, buffer layer 130, active coating 140 and the negative electrode 150 that stack gradually.
The material of buffer layer 130 can be poly-3,4-Ethylenedioxy Thiophene (PEDOT) and the mixture of polystyrene-sulfonic acid (PSS).Buffer layer 130 can omit, and active coating 140 is directly formed at the surface of anode 120.
The manufacturing processed of this organic solar batteries equipment 100, comprises the steps:
Step 1, on substrate 110, form anode 120.
Step 2, on anode 120, form buffer layer 130, the material of buffer layer 130 is the mixture of PEDOT and PSS, and wherein, PEDOT and PSS in mass ratio 6:1 mix.
Step 3, on buffer layer 130, form active coating 140, this active coating 140 comprises electron donor material and electron acceptor material, and electron donor material is phenyl-difluoride thiadiazolyl group multipolymer prepared by the present invention.
Wherein, the mol ratio of electron donor material and electron acceptor material is 1:2.Electron acceptor material can be PCBM.
Step 4, on active coating 140, form negative electrode 150.
Wherein, adopt vacuum vapour deposition on active coating 140, to form negative electrode 150, the material of negative electrode 150 is aluminium lamination, and aluminum layer thickness is 170nm.
After step 5, this organic solar batteries device 100 are stacked, under 110 ℃ of air tight conditions, heat 4 hours, then drop to room temperature.
After organic solar batteries device 100 is annealed, can effectively increase order and the regularity between the interior each group of molecule and molecule segment, arranged, improve transmission speed and the efficiency of carrier mobility, improve photoelectric transformation efficiency.
When this organic solar batteries device 100 uses, under illumination, light transmission substrate 110 and anode 120, the conduction hole type organic solar battery material in active coating 140 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by 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 transmit along electron acceptor material to negative electrode 150 and be collected by negative electrode 150, transmit and collected by anode 120 along electron donor material anode 120 in hole freely, thereby form photoelectric current and photovoltage, realizes opto-electronic conversion, when external load, can power to it.In this process, conduction hole type organic solar battery material phenyl-difluoride thiadiazolyl group multipolymer, because it has very wide spectral response range, can utilize luminous energy more fully, to obtain higher photoelectric transformation efficiency, increase the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of organic solar batteries device, and can make by technology such as spin coatings, be convenient to large batch of preparation.
Below in conjunction with specific embodiment, the invention will be further elaborated.
Embodiment 1
The preparation of poly-{ 4,4-di-n-octyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-5,6-bis-is fluoro-4,7-bis-(5-base-thiophene-2-yl) diazosulfide } (referred to as P1).
Above-mentioned phenyl-difluoride thiadiazolyl group copolymer p 1 are prepared by following reaction formula:
By 2 of 146mg, 6-bis-tin trimethyl-4,4-di-n-octyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene (0.2mmol), 88mg 5,6-bis-fluoro-4,7-bis-(the bromo-thiophene-2-of 5-yl) diazosulfide (0.2mmol) adds in the flask that fills 10mL toluene solvant, vacuumize deoxygenation and be filled with argon gas, then add the bi triphenyl phosphine dichloride palladium (0.008mmol) of 5.6mg, at 100 ℃, carry out Stille coupled reaction 36h.After reaction finishes, solution in flask is cooled to room temperature, carry out sedimentation to dripping 50mL methyl alcohol in flask, filter, be precipitated, gained precipitation adopts soxhlet extraction to use successively methyl alcohol and the each extracting 24h of normal hexane, be precipitated to colourless with chloroform extracting afterwards, collect chloroformic solution and be spin-dried for and obtain red powder, obtaining phenyl-difluoride thiadiazolyl group copolymer p 1 after collection under vacuum after 50 ℃ of dry 24h, productive rate is 83%.
The test result of phenyl-difluoride thiadiazolyl group copolymer p 1 is: Molecular weight (GPC, THF, R.I): M
n=39.2kDa, M
w/ M
n=2.2.
Refer to Fig. 3, Fig. 3 is the ultraviolet-visible absorption spectroscopy figure of phenyl-difluoride thiadiazolyl group copolymer p 1.As shown in Figure 3: this phenyl-difluoride thiadiazolyl group copolymer p 1 have large wider absorption between 300nm ~ 700nm, and wherein maximum absorption band is positioned at 606nm left and right.Illustrate that introducing two thiophene has widened absorption spectrum, this phenyl-difluoride thiadiazolyl group copolymer p 1 have demonstrated good photovoltaic performance.
Embodiment 2
The preparation of poly-{ 4,4-dimethylcyclopentane [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-5,6-bis-is fluoro-4,7-bis-(5-base-thiophene-2-yl) diazosulfide } (referred to as P2).
Above-mentioned phenyl-difluoride thiadiazolyl group copolymer p 2 are prepared by following reaction formula:
By 2 of 159mg, 6-bis-tin trimethyl-4, 4-dimethylcyclopentane [2, 1-b:3, 4-b '] 1,4-Dithiapentalene (0.3mmol), 5 of 148mg, 6-bis-fluoro-4, 7-bis-(the bromo-thiophene-2-of 5-yl) diazosulfide (0.3mmol) and 15mL tetrahydrofuran (THF) join in the two-mouth bottle of 50mL specification, after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then the tetra-triphenylphosphine palladium of 4mg (0.003mmol) is joined in two-mouth bottle, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, carry out Stille coupled reaction 60h at 70 ℃.After reaction finishes, solution in two-mouth bottle is cooled to room temperature, in two-mouth bottle, add 40mL methyl alcohol precipitating, filter, be precipitated, gained precipitation adopts soxhlet extraction to use successively methyl alcohol and the each extracting 24h of normal hexane, be precipitated to colourless with chloroform extracting afterwards, collect chloroformic solution and be spin-dried for and obtain red powder, obtaining phenyl-difluoride thiadiazolyl group copolymer p 2 after collection under vacuum after 50 ℃ of dry 24h, productive rate is 82%.
The test result of phenyl-difluoride thiadiazolyl group copolymer p 2 is: Molecular weight (GPC, THF, R.I): M
n=45.3kDa, M
w/ M
n=2.3.
Embodiment 3
The preparation of poly-{ 4,4-, bis-NSC 62789 basic ring pentane [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-5,6-bis-is fluoro-4,7-bis-(5-base-thiophene-2-yl) diazosulfide } (referred to as P3).
Above-mentioned phenyl-difluoride thiadiazolyl group copolymer p 3 are prepared by following reaction formula:
By 2 of 320mg, 6-bis-tin trimethyl-4,4-bis-NSC 62789 basic ring pentanes [2,1-b:3,4-b '] 1,4-Dithiapentalene (0.3mmol), 163mg 5,6-bis-fluoro-4,7-bis-(the bromo-thiophene-2-of 5-yl) diazosulfide (0.33mmol), the palladium (0.015mmol) of 3.5mg and three (o-methoxyphenyl) phosphine (0.06mmol) of 21mg join the N that fills 12mL, in the flask of dinethylformamide, in flask, lead to after the about 20min of nitrogen purge gas subsequently, carry out Stille coupled reaction 6h at 130 ℃.After reaction finishes, solution in flask is cooled to room temperature, in flask, add 40mL methyl alcohol precipitating, filter, be precipitated, gained precipitation adopts soxhlet extraction to use successively methyl alcohol and the each extracting 24h of normal hexane, be precipitated to colourless with chloroform extracting afterwards, collect chloroformic solution and be spin-dried for and obtain red powder, obtaining phenyl-difluoride thiadiazolyl group copolymer p 3 after collection under vacuum after 50 ℃ of dry 24h, productive rate is 75%.
The test result of phenyl-difluoride thiadiazolyl group copolymer p 3 is: Molecular weight (GPC, THF, R.I): M
n=98.1kDa, M
w/ M
n=2.0.
Embodiment 4
The preparation of poly-{ 4,4-, bis-normal butane basic ring pentane [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-5,6-bis-is fluoro-4,7-bis-(5-base-thiophene-2-yl) diazosulfide } (referred to as P4).
Above-mentioned phenyl-difluoride thiadiazolyl group copolymer p 4 are prepared by following reaction formula:
By 2 of 185mg, 6-bis-tin trimethyl-4, 4-bis-NSC 62789 basic ring pentanes [2, 1-b:3, 4-b '] 1,4-Dithiapentalene (0.3mmol), 5 of 178mg, 6-bis-fluoro-4, 7-bis-(the bromo-thiophene-2-of 5-yl) diazosulfide (0.36mmol), three or two argon benzyl acetone two palladiums (0.009mmol) of 9mg and the 2-dicyclohexyl phosphine-2 ' of 29mg, 6 '-dimethoxy-biphenyl (0.072mmol) joins the N that fills 12mL, in the flask of dinethylformamide, in flask, lead to after the about 20min of nitrogen purge gas subsequently, at 120 ℃, carry out Stille coupled reaction 24h.After reaction finishes, solution in flask is cooled to room temperature, in flask, add 40mL methyl alcohol precipitating, filter, be precipitated, gained precipitation adopts soxhlet extraction to use successively methyl alcohol and the each extracting 24h of normal hexane, be precipitated to colourless with chloroform extracting afterwards, collect chloroformic solution and be spin-dried for and obtain red powder, obtaining phenyl-difluoride thiadiazolyl group copolymer p 4 after collection under vacuum after 50 ℃ of dry 24h, productive rate is 79%.
The test result of phenyl-difluoride thiadiazolyl group copolymer p 4 is: Molecular weight (GPC, THF, R.I): M
n=74.6kDa, M
w/ M
n=2.0.
Embodiment 5
The preparation of poly-{ 4,4-, bis-dodecyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-5,6-bis-is fluoro-4,7-bis-(5-base-thiophene-2-yl) diazosulfide } (referred to as P5).
Above-mentioned phenyl-difluoride thiadiazolyl group copolymer p 5 are prepared by following reaction formula:
By 2 of 252mg, 6-bis-tin trimethyl-4, 4-bis-dodecyl pentamethylene [2, 1-b:3, 4-b '] 1,4-Dithiapentalene (0.3mmol), 5 of 148mg, 6-bis-fluoro-4, 7-bis-(the bromo-thiophene-2-of 5-yl) diazosulfide (0.3mmol) and 15mL toluene join in the two-mouth bottle of 50mL specification, after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then the tetra-triphenylphosphine palladium of 8mg (0.006mmol) is joined in two-mouth bottle, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, at 90 ℃, carry out Stille coupling reaction 48h.After reaction finishes, solution in two-mouth bottle is cooled to room temperature, in two-mouth bottle, add 40mL methyl alcohol precipitating, filter, be precipitated, gained precipitation adopts soxhlet extraction to use successively methyl alcohol and the each extracting 24h of normal hexane, be precipitated to colourless with chloroform extracting afterwards, collect chloroformic solution and be spin-dried for and obtain red powder, obtaining phenyl-difluoride thiadiazolyl group copolymer p 5 after collection under vacuum after 50 ℃ of dry 24h, productive rate is 82%.
The test result of phenyl-difluoride thiadiazolyl group copolymer p 5 is: Molecular weight (GPC, THF, R.I): M
n=67.4kDa, M
w/ M
n=2.1.
Embodiment 6
A manufacturing processed for organic solar batteries device, comprises the following steps:
Step 1, at substrate formation anode on glass.
Step 2, on anode, form buffer layer, the material of buffer layer is the mixture of PEDOT and PSS, and wherein, PEDOT and PSS in mass ratio 6:1 mix.
Step 3, on buffer layer, form active coating, this active coating comprises electron donor material and electron acceptor material, and electron acceptor material is PCBM, and electron donor material is phenyl-difluoride thiadiazolyl group copolymer p 1 prepared by embodiment 1.The mol ratio of P1 and PCBM is 1:2.
Step 4, on active coating, form negative electrode.
Adopt vacuum vapour deposition, form negative electrode on active coating, negative electrode is that thickness is the aluminium lamination of 170nm.
Step 5, this organic solar batteries device layer poststack heat 4 hours, then drop to room temperature under 110 ℃ of air tight conditions.
At 100mW/cm
2under (AM 1.5G) illumination, the optical property of having tested the organic solar batteries device of embodiment 6.Result shows: the effciency of energy transfer 4.1% of the body heterojunction solar cell device that phenyl-difluoride thiadiazolyl group copolymer p 1 are donor material.Illustrate that phenyl-difluoride thiadiazolyl group copolymer p 1 have improved the effciency of energy transfer of organic solar batteries device.
Embodiment 7
A manufacturing processed for solar cell device, comprises the following steps:
Step 1, at substrate formation anode on glass.
Step 2, on anode, form buffer layer, the material of buffer layer is the mixture of PEDOT and PSS, and wherein, PEDOT and PSS in mass ratio 6:1 mix.
Step 3, on buffer layer, form active coating, this active coating comprises electron donor material and electron acceptor material, and electron acceptor material is PCBM, and electron donor material is phenyl-difluoride thiadiazolyl group copolymer p 2 prepared by embodiment 2.The mol ratio of P2 and PCBM is 1:2.
Step 4, on active coating, form negative electrode.
Adopt vacuum vapour deposition, form negative electrode on active coating, negative electrode is that thickness is the aluminium lamination of 170nm.
After step 5, this solar cell device are stacked, under 110 ℃ of air tight conditions, heat 4 hours, then drop to room temperature.
At 100mW/cm
2under (AM 1.5G) illumination, the optical property of having tested the organic solar batteries device of embodiment 7.Result shows: the effciency of energy transfer 3.9% of the body heterojunction solar cell device that phenyl-difluoride thiadiazolyl group copolymer p 2 are donor material.Illustrate that phenyl-difluoride thiadiazolyl group copolymer p 2 have improved the effciency of energy transfer of organic solar batteries device.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. phenyl-difluoride a thiadiazolyl group multipolymer, is characterized in that, has following structural formula:
Wherein, R is selected from C
1~ C
20alkyl, the integer that n is 10 ~ 100.
2. a preparation method for phenyl-difluoride thiadiazolyl group multipolymer, is characterized in that, comprises the following steps:
Raw material A and raw material B as follows is provided respectively:
Under the atmosphere of shielding gas; after the raw material A that is 1:1 ~ 1.2 by mol ratio and raw material B, catalyzer and organic solvent mix; at 70 ℃ ~ 130 ℃, react 6h ~ 60h, after separating-purifying, must there is phenyl-difluoride the thiadiazolyl group multipolymer of following structural formula:
Wherein, the integer that n is 10 ~ 100.
3. the preparation method of phenyl-difluoride according to claim 2 thiadiazolyl group multipolymer, is characterized in that, described shielding gas is the gas mixture of argon gas, nitrogen or nitrogen and argon gas.
4. the preparation method of phenyl-difluoride according to claim 2 thiadiazolyl group multipolymer, is characterized in that, the mol ratio of described catalyzer and described raw material A is 1:20 ~ 1:100; Described catalyzer is the mixture of organic palladium or organic palladium and organophosphorus ligand; Described organic palladium is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, the mixture of described organic palladium and organophosphorus ligand is mixture or three or two argon benzyl acetone two palladiums and the 2-dicyclohexyl phosphine-2 ' of palladium and three (o-methoxyphenyl) phosphine, the mixture of 6 '-dimethoxy-biphenyl; In the mixture of described organic palladium and organophosphorus ligand, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 8.
5. the preparation method of phenyl-difluoride according to claim 2 thiadiazolyl group multipolymer, is characterized in that, described organic solvent is at least one in toluene, DMF and tetrahydrofuran (THF).
6. the preparation method of phenyl-difluoride according to claim 2 thiadiazolyl group multipolymer, is characterized in that, temperature of reaction is 90 ℃ ~ 120 ℃, and the reaction times is 12h ~ 48h.
7. the preparation method of phenyl-difluoride according to claim 2 thiadiazolyl group multipolymer, it is characterized in that, after described separating-purifying comprises the steps: that reaction finishes, reacted solution is cooled to room temperature, adds methyl alcohol precipitating, filter, gained precipitation adopts soxhlet extraction to use successively methyl alcohol and normal hexane extracting, be precipitated to afterwards colourlessly with chloroform extracting, collect chloroformic solution and be spin-dried for and obtain red powder, described red powder is dry under vacuum.
8. an organic solar batteries device, comprises the substrate, anode, buffer layer, active coating and the negative electrode that stack gradually, it is characterized in that, described active coating comprises phenyl-difluoride the thiadiazolyl group multipolymer with following structural formula:
Wherein, R is selected from C
1~ C
20alkyl, the integer that n is 10 ~ 100.
9. organic solar batteries device according to claim 8, is characterized in that, the material of described buffer layer is the mixture of poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid.
10. organic solar batteries device according to claim 8, is characterized in that, described negative electrode adopts aluminium electrode or double-metal layer electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210450648.XA CN103804650A (en) | 2012-11-12 | 2012-11-12 | Difluorobenzothiadiazole-based copolymer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210450648.XA CN103804650A (en) | 2012-11-12 | 2012-11-12 | Difluorobenzothiadiazole-based copolymer and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103804650A true CN103804650A (en) | 2014-05-21 |
Family
ID=50702077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210450648.XA Pending CN103804650A (en) | 2012-11-12 | 2012-11-12 | Difluorobenzothiadiazole-based copolymer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103804650A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565939A (en) * | 2015-10-10 | 2017-04-19 | 南京欧纳壹有机光电有限公司 | Semi-conducting polymers capable of electronic printing and applications thereof |
| US10516111B2 (en) | 2013-12-26 | 2019-12-24 | The Hong Kong University Of Science And Technology | Polymer/fullerene formations and their use in electronic/photonic devices |
-
2012
- 2012-11-12 CN CN201210450648.XA patent/CN103804650A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10516111B2 (en) | 2013-12-26 | 2019-12-24 | The Hong Kong University Of Science And Technology | Polymer/fullerene formations and their use in electronic/photonic devices |
| CN106565939A (en) * | 2015-10-10 | 2017-04-19 | 南京欧纳壹有机光电有限公司 | Semi-conducting polymers capable of electronic printing and applications thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104017187A (en) | Isoindigo group-containing polymer as well as preparation method and application thereof | |
| CN104513367A (en) | Quinoxaline based copolymer, preparation method and applications thereof | |
| CN104513370A (en) | Diketopyrrolo pyrrole based copolymer, preparation method, and applications thereof | |
| CN103804650A (en) | Difluorobenzothiadiazole-based copolymer and preparation method and application thereof | |
| CN103665339A (en) | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof | |
| CN104177600A (en) | Polymer containing dithiazolebenzothiadiazole group, preparation method and organic solar cell device thereof | |
| CN104592497A (en) | Dithienylethylene-based copolymer solar battery material, and preparation method and application thereof | |
| CN103804649A (en) | Thiophthene-based copolymer as well as preparation method and application thereof | |
| CN103804644A (en) | Benzothiazolyl copolymer as well as preparation method and application thereof | |
| CN103159928A (en) | Thiophene pyrroledione based co-polymer material, and preparation method and application thereof | |
| CN104292432A (en) | Polymer containing difluorobenzotriazole unit, and preparation method and application thereof | |
| CN104513361A (en) | Anthraquinone based copolymer, preparation method and applications thereof | |
| CN104629003A (en) | Isoindigo group containing polymer, preparation method and organic solar cell device | |
| CN104513369A (en) | Quinoxaline based copolymer, preparation method and applications thereof | |
| CN103665338A (en) | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof | |
| CN104017182A (en) | Benzothiadiazolyl containing polymer and preparation method and application thereof | |
| CN104250365A (en) | Anthraquinonyl group-containing polymer, preparation method thereof, and organic solar cell device | |
| CN104292429A (en) | Anthraquinonyl-containing polymer, preparation method thereof and organic solar cell device | |
| CN103665336A (en) | Benzothiazole-containing unit polymer, preparation method and application thereof | |
| CN103159917A (en) | Thiophene pyrroledione based co-polymer organic semiconductor material, and preparation method and application thereof | |
| CN104017181A (en) | Naphtho-dithienyl containing polymer and preparation method and application thereof | |
| CN104177594A (en) | Benzo dithienyl-containing polymer and preparation method thereof and organic solar energy cell device | |
| CN104017178A (en) | Polymer containing diketopyrrolopyrrole group as well as preparation method and application thereof | |
| CN104177598A (en) | Polymer containing cyclopentanodithiophene group, preparation method and organic solar cell device thereof | |
| CN104513368A (en) | Quinoxaline based copolymer, preparation method and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140521 |