CN102850525B - Containing the organic semiconductor material of benzotriazole base, its preparation method and organic solar batteries - Google Patents
Containing the organic semiconductor material of benzotriazole base, its preparation method and organic solar batteries Download PDFInfo
- Publication number
- CN102850525B CN102850525B CN201110182384.XA CN201110182384A CN102850525B CN 102850525 B CN102850525 B CN 102850525B CN 201110182384 A CN201110182384 A CN 201110182384A CN 102850525 B CN102850525 B CN 102850525B
- Authority
- CN
- China
- Prior art keywords
- benzotriazole
- semiconductor material
- organic semiconductor
- preparation
- base
- 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.)
- Active
Links
- 0 CC(C)c1ccc(C(C=NN(*)N)=CC=C)[s]1 Chemical compound CC(C)c1ccc(C(C=NN(*)N)=CC=C)[s]1 0.000 description 2
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 belongs to field of photovoltaic materials, it discloses a kind of organic semiconductor material containing benzotriazole base, its preparation method and organic solar batteries; Following general structural formula should be had containing the organic semiconductor material of benzotriazole base:
in above-mentioned formula, R
1, R
2for C
1~ C
20alkyl; N is the integer of 10 ~ 50.Two thiophene benzotriazoles and carbazole diene are passed through Heck coupling polymerization, have widened the absorption band of polycarbazole by the organic semiconductor material containing benzotriazole base of the present invention, improve its utilization ratio to sunlight, obtain better photovoltaic performance.
Description
Technical field
The invention belongs to field of photovoltaic materials, relate to a kind of organic semiconductor material containing benzotriazole base specifically.The invention still further relates to the organic solar batteries that these preparation method and application containing the organic semiconductor material of benzotriazole base should contain the organic semiconductor material of benzotriazole base.
Background technology
Sun power is the optimal substitute energys of the following mankind, is that the solar cell of electric energy is also the focus studied by solar energy converting; The conjugated polymer thin films solar cell of rising in recent years has that cost is low, lightweight, manufacture craft simple, can be prepared into the outstanding advantages such as flexible device.In addition, organic materials is of a great variety, designability is strong, is hopeful by the design of material and optimizes the performance improving solar cell.
Polycarbazole derivative is the classical material that one can be used for polymer LED (PLED) and polymer solar battery.From absorption spectrum, their maximum absorption wavelengths are at 500nm, and contrast with solar spectrum and can find out that this material is obviously not enough to the absorption of sunlight, sunlight utilization ratio is low; Therefore, design and synthesis narrow band gap polycarbazole becomes important research direction.
Summary of the invention
The object of the present invention is to provide a kind of organic semiconductor material containing benzotriazole base that can improve sunlight utilization ratio.
A kind of organic semiconductor material containing benzotriazole base with following general structural formula:
In above-mentioned formula, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl; N is more than or equal to the integer that 10 are less than or equal to 50.
Another object of the present invention is to the preparation method providing the above-mentioned organic semiconductor material containing benzotriazole base, its preparation technology is as follows:
S1, the compd A that following structural formula is provided respectively and compd B:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl;
In S2, oxygen-free environment, by described compd A and B with 1: 1 mol ratio join in the organic solvent containing catalyzer, at 90 ~ 120 DEG C, carry out Heck coupling reaction 24 ~ 72h, obtaining following general structure is the organic semiconductor material containing benzotriazole base represented:
In above-mentioned formula, n is more than or equal to the integer that 10 are less than or equal to 50.
Described preparation method also comprises the purification step to the organic semiconductor material containing benzotriazole base that step S2 obtains:
After S3, step S2 reaction terminates, in step S2, drip methyl alcohol, containing the organic semiconductor material of benzotriazole base described in precipitating; Secondly filtered by apparatus,Soxhlet's, and screening is used successively methyl alcohol and normal hexane extracting 24h; Then be that solvent carries out extracting process with chloroform, obtain the described organic semiconductor material containing benzotriazole base of purifying.
In the step S1 of above-mentioned preparation method, described compd B adopts following steps to obtain:
By general structure be
compound C be dissolved in the mixed solution of trichloromethane and Glacial acetic acid; Then N-bromo-succinimide is added, and after at room temperature reacting 12h, obtained described compd B.
In preparation process for above-claimed cpd B, also comprise the purification step to described compd B:
Reaction mixture dichloromethane extraction containing described compd B is washed with water again; Then desolventizing with revolving after anhydrous magnesium sulfate drying to boil off, obtaining the described compd B of purifying.
In the step S2 of above-mentioned preparation method, the molar weight of described catalyzer is 0.5% ~ 10% of the mole dosage of described compd A; Described catalyzer is the mixture of tetra-triphenylphosphine palladium, bi triphenyl phosphorus palladium chloride or palladium and three (adjacent methyl) Phenylphosphine; In the mixture of described palladium and three (adjacent methyl) Phenylphosphine, the molar weight of described palladium is 0.5% ~ 10% of described compd A, and the molar weight of described three (adjacent methyl) Phenylphosphine is 4 ~ 10 times of the molar weight of described palladium.
In the step S2 of above-mentioned preparation method, described organic solvent is toluene, chlorobenzene, tetrahydrofuran (THF) or DMF.
Another goal of the invention of the present invention is to provide a kind of organic solar batteries, comprise the glass-base, transparent anode, middle supplementary layer, active coating and the negative electrode that stack gradually, described middle supplementary layer adopts poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material, described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material adopts [6,6] phenyl-C
61-methyl-butyrate; Wherein, described electron donor material selects the organic semiconductor material containing benzotriazole base as claimed in claim 1.
Organic semiconductor material containing benzotriazole base provided by the invention, 1,2,3-benzotriazole is an important electron acceptor(EA) unit, and it has two strong electrophilic imido grpups, is the heterogeneous ring compound having strong electrophilic performance, simultaneously, enough easy the modification with functional groups such as other alkyl flexible chains of N-H bond energy on 1,2,3-benzotriazole regulates solvability and photoelectric properties; Containing the organic semiconductor material of benzotriazole base, two thiophene benzotriazoles (DTBTz) and carbazole diene should be passed through Heck coupling polymerization, widen the absorption band of polycarbazole, improve its utilization ratio to sunlight, obtain better photovoltaic performance.
Accompanying drawing explanation
Fig. 1 is the abosrption spectrogram of the organic semiconductor material containing benzotriazole base of embodiment 1;
Fig. 2 is the structure iron of the organic solar batteries of embodiment 6.
Embodiment
The organic semiconductor material containing benzotriazole base of one embodiment, has following general structural formula:
In above-mentioned formula, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl; N is more than or equal to the integer that 10 are less than or equal to 50, and namely n is the integer of 10 ~ 50.
Above-mentioned containing in the organic semiconductor material of benzotriazole base, 1,2,3-benzotriazole is an important electron acceptor(EA) unit, and it has two strong electrophilic imido grpups, is the heterogeneous ring compound having strong electrophilic performance, simultaneously, enough easy the modification with functional groups such as other alkyl flexible chains of N-H bond energy on 1,2,3-benzotriazole regulates solvability and photoelectric properties; Containing the organic semiconductor material of benzotriazole base, two thiophene benzotriazoles (DTBTz) and carbazole diene should be passed through Heck coupling polymerization, widen the absorption band of polycarbazole, improve its utilization ratio to sunlight, obtain better photovoltaic performance.
The preparation method of the organic semiconductor material containing benzotriazole base of one embodiment, it comprises the steps:
Step S1, the compd A that following structural formula is provided respectively and compd B:
Wherein, in compd A, R
1for C
1~ C
20alkyl; In compd B, R
2for C
1~ C
20alkyl;
(be made up of inert atmosphere in step S2, oxygen-free environment, as nitrogen atmosphere or argon gas atmosphere), by described compd A and B with 1: 1 mol ratio join in the organic solvent containing catalyzer, at 90 ~ 120 DEG C, carry out Heck coupling reaction 24 ~ 72h, obtain the organic semiconductor material containing benzotriazole base of following general structure:
In above-mentioned formula, n is more than or equal to the integer that 10 are less than or equal to 50; Reaction formula is as follows:
Preferably, described preparation method also comprises the purification step to the organic semiconductor material containing benzotriazole base that step S2 obtains:
After step S3, step S2 reaction terminates, in the reaction mixture in step S2, drip methyl alcohol, containing the organic semiconductor material of benzotriazole base described in precipitating; Secondly filtered by apparatus,Soxhlet's, and screening is used successively methyl alcohol and normal hexane extracting 24h; Then be solvent extraction with chloroform, obtain the described organic semiconductor material containing benzotriazole base of purifying.
In the step S1 of above-mentioned preparation method, described compd A can directly be buied from the market.Described compd B adopts following steps to obtain:
By general structure be
compound C (that is, 2-alkyl-4,7-bis-thiophene-1,2,3-benzotriazole) be dissolved in trichloromethane (CHCl
3) and Glacial acetic acid (AcOH) mixed solution in; Then N-bromo-succinimide (NBS) is added, and after at room temperature reacting 12h, obtained described compd B; Reaction formula is as follows:
Preferably, in the preparation process of described compd B, also comprise the step of obtained compd B being carried out to purifying:
Reaction mixture dichloromethane extraction containing described compd B is washed with water again; Then desolventizing with revolving after anhydrous magnesium sulfate drying to boil off, obtaining the described compd B of purifying.
In the step S2 of above-mentioned preparation method, the molar weight of described catalyzer is 0.5% ~ 10% of the mole dosage of described compd A; Described catalyzer is the mixture of tetra-triphenylphosphine palladium, bi triphenyl phosphorus palladium chloride or palladium and three (adjacent methyl) Phenylphosphine; In the mixture of described palladium and three (adjacent methyl) Phenylphosphine, the molar weight of described palladium is 0.5% ~ 10% of described compd A, and the molar weight of described three (adjacent methyl) Phenylphosphine is 4 ~ 10 times of the molar weight of described palladium.
In the step S2 of above-mentioned preparation method, described organic solvent is toluene, chlorobenzene, tetrahydrofuran (THF) or DMF.
Organic solar batteries provided by the invention, comprise the glass-base, transparent anode, middle supplementary layer, active coating and the negative electrode that stack gradually, described transparent anode adopts tin indium oxide (ITO), described middle supplementary layer adopts poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material, described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material adopts [6,6] phenyl-C
61-methyl-butyrate, described cathode layer adopts aluminium lamination; Wherein, described electron donor material selects structural formula to be
(wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl; N is more than or equal to the integer that 10 are less than or equal to 50) containing the organic semiconductor material of benzotriazole base.
Below in conjunction with accompanying drawing, embodiment is described in further detail.
Below in each embodiment, compd A is directly buied from the market.
Embodiment 1
The organic semiconductor material containing benzotriazole base of the present embodiment 1, i.e. poly-{ 3,6-divinyl-N-octylcarbazol-2-octyl group-4,7-bis-thiophene-1,2,3-benzotriazole } (wherein, R
1for octyl group, R
2for octyl group, n is 25), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
The preparation of step one, 2-octyl group-4,7-bis-(5,5 '-dibromo thiophene base)-1,2,3-benzotriazoles, reaction formula is as follows:
Detailed process is as follows: under lucifuge condition, by compound 2-octyl group-4,7-bis-thiophene-1,2,3-benzotriazole (2.37g, 6mmol) be dissolved in trichloromethane (60mL) and Glacial acetic acid (60mL) mixed solution, move in ice bath, then N-bromo-succinimide (2.35g, 13.2mmol) is added wherein in batches, after at room temperature reacting 12h, obtain reaction mixture.
Dichloromethane extraction reaction mixture washes with water for three times again, merges organic phase, with revolving steaming solvent after anhydrous magnesium sulfate drying.Crude product DMF recrystallization obtains the pure product of yellow needle-like crystals, and productive rate is 75%.
1H NMR(400MHz，CDCl
3，ppm)：7.79(d，2H)，7.51(s，2H)，7.13(d，2H)，4.80(t，2H)，2.18(m，2H)，1.41-1.27(m，10H)，0.87(t，3H).
The preparation of step 2, poly-{ 3,6-divinyl-N-octylcarbazol-2-octyl group-4,7-bis-thiophene-1,2,3-benzotriazole }, reaction formula is as follows:
Under nitrogen protection; monomer 3; 6-divinyl-N-octylcarbazol (166mg; 0.5mmol) with monomer benzene 2-octyl group-4; 7-bis-(5-bromothiophene base)-1,2,3-benzotriazole (277mg; 0.5mmol) and three (adjacent methyl) Phenylphosphine (37mg, 0.12mmol) put into two mouthfuls of flasks of 50mL.By DMF (6mL) and triethylamine (2mL), after fully logical nitrogen purge gas is about 10min, then add palladium (4.5mg, 0.02mmol).After fully logical nitrogen purge gas is about 20min again, stirring reaction 24h 90 DEG C time, and then at 110 DEG C, continue reaction 24h, obtain reaction mixture.
Stop polyreaction after cooling, drip 30mL methyl alcohol precipitating to the reaction mixture in flask, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain dark red solid, after collection, be polymkeric substance after 40 DEG C of dry 24h under vacuo.Productive rate is 67%.
GPC：M
n＝18600，PDI＝2.0.
Fig. 1 is the abosrption spectrogram of the organic semiconductor material containing benzotriazole base of the embodiment of the present invention 1; As shown in Figure 1, the polymkeric substance in the embodiment of the present invention 1 to the absorption region of sunlight is: 300nm ~ 650nm; Wherein, absorb the strongest to the sunlight that wavelength is 530nm.
Embodiment 2
The organic semiconductor material containing benzotriazole base of the present embodiment 2, i.e. poly-{ 3,6-divinyl-N-dodecyl carbazole-2-hexyl-4,7-bis-thiophene-1,2,3-benzotriazole } (wherein, R
1for dodecyl, R
2for hexyl, n is 32), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Step one, is with the difference of the step one in embodiment 1: hexyl replaces octyl group;
The preparation of step 2, poly-{ 3,6-divinyl-N-dodecyl carbazole-2-hexyl-4,7-bis-thiophene-1,2,3-benzotriazole }, reaction formula is as follows:
Under nitrogen protection; 3,6-divinyl-N-dodecyl carbazole (116mg, 0.3mmol); 2-n-hexyl-4; the bromo-benzotriazole (157.5mg, 0.3mmol) of 7-bis-and 10mL toluene join in the two-mouth bottle of 50mL respectively, after fully logical nitrogen purge gas is about 20min; then 15mg bi triphenyl phosphorus palladium chloride is added wherein; after fully logical nitrogen purge gas is about 10min again, at 120 DEG C of stirring reaction 12h, obtain reaction mixture.
Stop polyreaction after cooling, add 40mL methyl alcohol precipitating to the reaction mixture in flask, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, be polymkeric substance after 50 DEG C of dry 24h under vacuo.Productive rate is 65%.
GPC：M
n＝247800，PDI＝1.9.
Embodiment 3
The organic semiconductor material containing benzotriazole base of the present embodiment 3, i.e. poly-{ 3,6-divinyl-N-hexyl carbazole-2-eicosyl-4,7-bis-thiophene-1,2,3-benzotriazole } (wherein, R
1for hexyl, R
2for eicosyl, n is 10):
The preparation process of above-mentioned polymkeric substance is as follows:
Step one, is with the difference of the step one in embodiment 1: eicosyl replaces octyl group;
The preparation of step 2, poly-{ 3,6-divinyl-N-hexyl carbazole-2-eicosyl-4,7-bis-thiophene-1,2,3-benzotriazole }, reaction formula is as follows:
Under argon shield; 3,7-divinyl-N-hexyl phenothiazine (91mg, 0.3mmol); 2-eicosyl-4; the bromo-benzotriazole (216.6mg, 0.3mmol) of 7-bis-and 10mL tetrahydrofuran (THF) join in the two-mouth bottle of 50mL respectively, after fully logical argon gas air-discharging is about 20min; then 25mg tetra-triphenylphosphine is added wherein; after fully logical argon gas air-discharging is about 10min again, at 90 DEG C of stirring reaction 60h, obtain reaction mixture.
Stop polyreaction after cooling, add 40mL methyl alcohol precipitating to the reaction mixture in flask, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, be polymkeric substance after 50 DEG C of dry 24h under vacuo.Productive rate is 40%.
GPC：M
n＝10400，PDI＝2.1.
Embodiment 4
The present embodiment 4 containing benzotriazole base co-polymer, i.e. poly-{ 3,6-divinyl-N-eicosyl carbazole-2-methyl-4,7-bis-thiophene-1,2,3-benzotriazole } (wherein, R
1for eicosyl, R
2for methyl, n is 50):
The preparation process of above-mentioned polymkeric substance is as follows:
Step one, is with the difference of the step one in embodiment 1: methyl replaces octyl group
The preparation of step 2, poly-{ 3,6-divinyl-N-eicosyl carbazole-2-methyl-4,7-bis-thiophene-1,2,3-benzotriazole }, reaction formula is as follows:
Under nitrogen protection, monomer 3,6-divinyl-N-eicosyl carbazole (250mg; 0.5mmol) with monomer 2-methyl-4,7-bis-(5-bromothiophene base)-1,2; 3-benzotriazole (235mg, 0.5mmol) and P (o-toly)
3(three (adjacent methyl) Phenylphosphine), (60mg, 0.12mmol) puts into two mouthfuls of flasks of 50mL, adds after the fully logical nitrogen purge gas of chlorobenzene (10mL) is about 10min subsequently, add palladium (11.2mg, 0.05mmol) again.After fully logical nitrogen purge gas is about 20min again, stirring reaction 36h 100 DEG C time, and then at 110 DEG C, continue reaction 36h, obtain reaction mixture.
Stop polyreaction after cooling, drip 30mL methyl alcohol precipitating to the reaction mixture in flask, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain dark red solid, after collection, be polymkeric substance after 40 DEG C of dry 24h under vacuo.Productive rate is 87%.
GPC：M
n＝39800，PDI＝1.7。
Embodiment 5
The present embodiment 5 containing benzotriazole base co-polymer, i.e. poly-{ 3,6-divinyl-N-methyl carbazole-2-eicosyl-4,7-bis-thiophene-1,2,3-benzotriazole } (wherein, R
1for methyl, R
2for eicosyl, n is 43):
The preparation process of above-mentioned polymkeric substance is as follows:
Step one, is with the difference of the step one in embodiment 1: eicosyl replaces octyl group
The preparation of step 2, poly-{ 3,6-divinyl-N-methyl carbazole-2-eicosyl-4,7-bis-thiophene-1,2,3-benzotriazole }, reaction formula is as follows:
Under nitrogen protection; monomer 3; 6-divinyl-N-methyl carbazole (167mg; 0.5mmol) with monomer benzotriazole derivatives (2-eicosyl-4; 7-bis-(5-bromothiophene base)-1; 2,3-benzotriazole) (368mg, 0.5mmol) and P (o-toly)
3(three (adjacent methyl) Phenylphosphine), (76mg, 0.25mmol) puts into two mouthfuls of flasks of 50mL, adds after the fully logical nitrogen purge gas of tetrahydrofuran (THF) (12mL) is about 10min subsequently, add palladium (6mg, 0.025mmol) again.After fully logical nitrogen purge gas is about 20min again, 90 DEG C time, stirring reaction 72h obtains reaction mixture.
Stop polyreaction after cooling, drip 30mL methyl alcohol precipitating to the reaction mixture in flask, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain dark red solid, after collection, be polymkeric substance after 40 DEG C of dry 24h under vacuo.Productive rate is 75%.
GPC：M
n＝33400，PDI＝1.8。
Embodiment 6
The present embodiment 6 is with the organic semiconductor material containing benzotriazole base in embodiment 1, and namely poly-{ 3,6-divinyl-N-octylcarbazol-2-octyl group-4,7-bis-thiophene-1,2,3-benzotriazole } is as the active layer material of organic solar batteries.
As shown in Figure 2, this organic solar batteries comprises the glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14 and the negative electrode 15 that stack gradually; Wherein, 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, poly-{ 3, the 6-divinyl-N-octylcarbazol-2-octyl group-4 that electron donor material adopts embodiment 1 to prepare, 7-bis-thiophene-1,2,3-benzotriazole }, electron acceptor material can be [6,6] phenyl-C
61-methyl-butyrate (referred to as PCBM); Negative electrode 15 can adopt aluminium electrode; Glass-base 11 can be used as bottom, i.e. substrate.
When making above-mentioned solar cell, choose ito glass, and after ultrasonic cleaning, process with oxygen-Plasma, supplementary layer 13 in the middle of coating on ito glass, then multipolymer embodiment 1 prepared and electron acceptor material are coated on middle supplementary layer 13 after blended, 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 to heat 4 hours under 110 degrees Celsius of air tight conditions, drop to room temperature again, the order and regularity that arrange between each group and molecule segment in molecule effectively can be increased after device is annealed, improve transmission speed and the efficiency of carrier mobility, and then improve photoelectric transformation efficiency.In the present embodiment, the thickness of negative electrode 15 is 170nm, also can be 30nm, 130nm, 60nm.
This organic solar batteries heats 4 hours under 110 degrees Celsius of air tight conditions, drop to room temperature again, the order and regularity that arrange between each group and molecule segment in molecule effectively can be increased after device is annealed, improve transmission speed and the efficiency of carrier mobility, and then improve photoelectric transformation efficiency
As shown in Figure 2, under light illumination, light transmission glass-base 11 and ITO electrode 12, the Conduction cavity type electroluminescent material in active coating 14 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, thus 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, hole is along electron donor material to ito anode transmission and collected by anode freely, thus forms photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In the process, Conduction cavity type electroluminescent material has very wide spectral response range due to it, can utilize luminous energy more fully, 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 be made by technology such as spin coatings, be convenient to large batch of preparation.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (3)
1., containing an organic semiconductor material for benzotriazole base, there is following general structural formula:
In above formula, R
1for C
8h
17-, R
2for C
8h
17-; N is 25.
2., containing a preparation method for the organic semiconductor material of benzotriazole base, it is characterized in that, described preparation method comprises the steps:
Containing the organic semiconductor material of benzotriazole base, i.e. poly-{ 3,6-divinyl-N-octylcarbazol-2-octyl group-4,7-bis-thiophene-1,2,3-benzotriazole }, its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
The preparation of step one, 2-octyl group-4,7-bis-(5-bromothiophene base)-1,2,3-benzotriazoles, reaction formula is as follows:
Detailed process is as follows: under lucifuge condition, by the compound 2-octyl group-4 of 6mmol, 7-bis-thiophene-1,2,3-benzotriazole is dissolved in 60mL trichloromethane and 60mL Glacial acetic acid mixed solution, moves in ice bath, is then added wherein by 13.2mmol N-bromo-succinimide in batches, after at room temperature reacting 12h, obtain reaction mixture;
Dichloromethane extraction reaction mixture washes with water for three times again, and merge organic phase, with revolving steaming solvent after anhydrous magnesium sulfate drying, crude product DMF recrystallization obtains the pure product of yellow needle-like crystals, and productive rate is 75%;
The preparation of step 2, poly-{ 3,6-divinyl-N-octylcarbazol-2-octyl group-4,7-bis-thiophene-1,2,3-benzotriazole }, reaction formula is as follows:
Under nitrogen protection, monomer 3, the 6-divinyl-N-octylcarbazol of 0.5mmol and monomer 2-octyl group-4,7-bis-(the 5-bromothiophene base)-1 of 0.5mmol, three (adjacent methyl) Phenylphosphine of 2,3-benzotriazole and 0.12mmol puts into two mouthfuls of flasks of 50mL; By 6mL DMF and 2mL triethylamine, after fully logical nitrogen purge gas 10min, add 0.02mmol palladium again, then after fully logical nitrogen purge gas 20min, stirring reaction 24h 90 DEG C time, and then at 110 DEG C, continue reaction 24h, obtain reaction mixture;
Polyreaction is stopped after cooling, 30mL methyl alcohol precipitating is dripped to the reaction mixture in flask, methyl alcohol and normal hexane extracting 24h is used successively after being filtered by apparatus,Soxhlet's, then be that solvent extraction is to colourless with chloroform, collect chloroformic solution and be spin-dried for and obtain dark red solid, after collection, being polymkeric substance after 40 DEG C of dry 24h under vacuo.
3. an organic solar batteries, comprise the glass-base, transparent anode, middle supplementary layer, active coating and the negative electrode that stack gradually, described middle supplementary layer adopts poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material, described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material adopts [6,6] phenyl-C
61-methyl-butyrate; It is characterized in that, the electron donor material of described active coating is as claimed in claim 1 containing the organic semiconductor material of benzotriazole base.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110182384.XA CN102850525B (en) | 2011-06-30 | 2011-06-30 | Containing the organic semiconductor material of benzotriazole base, its preparation method and organic solar batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110182384.XA CN102850525B (en) | 2011-06-30 | 2011-06-30 | Containing the organic semiconductor material of benzotriazole base, its preparation method and organic solar batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102850525A CN102850525A (en) | 2013-01-02 |
| CN102850525B true CN102850525B (en) | 2015-09-23 |
Family
ID=47397539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110182384.XA Active CN102850525B (en) | 2011-06-30 | 2011-06-30 | Containing the organic semiconductor material of benzotriazole base, its preparation method and organic solar batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102850525B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912315A (en) * | 2018-07-24 | 2018-11-30 | 武汉工程大学 | A kind of benzo pair thiophene derivant class organic solar batteries two dimension donor materials and preparation method thereof that chlorine atom is modified |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935389A (en) * | 2010-07-20 | 2011-01-05 | 中南大学 | 2-thiophene-benzotriazole-based polymer materials and photovoltaic application thereof |
-
2011
- 2011-06-30 CN CN201110182384.XA patent/CN102850525B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935389A (en) * | 2010-07-20 | 2011-01-05 | 中南大学 | 2-thiophene-benzotriazole-based polymer materials and photovoltaic application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102850525A (en) | 2013-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103154057B (en) | Conjugated polymer containing isoindigo units, preparation method and use thereof | |
| CN102295754B (en) | Naphthalene tetracarboxylic diimide-naphtho dithiophene-containing copolymer and preparation method as well as application thereof | |
| CN114621275B (en) | Benzotriazole boron nitrogen derivative and application thereof | |
| CN102850526B (en) | Organic semiconductor material, its preparation method and organic solar batteries | |
| 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 | |
| JP5667693B2 (en) | Quinoxaline unit-containing porphyrin copolymer, method for producing the same, and application thereof | |
| CN102850525B (en) | Containing the organic semiconductor material of benzotriazole base, its preparation method and organic solar batteries | |
| CN102850527A (en) | Copolymer of N,N'-disubstituted isoindigo and fluorene and preparation method and application thereof | |
| CN102850522B (en) | Containing benzotriazole base co-polymer and its preparation method and application | |
| CN102850524A (en) | Copolymer containing benzotriazole group, preparation method thereof and organic solar cell | |
| CN102850523A (en) | Photoelectric material containing benzotriazolyl, its preparation method and organic solar cell | |
| CN103159919B (en) | Cyano group anthraquinonyl multipolymer solar cell material and its preparation method and application | |
| EP2578592A1 (en) | Quinoid silafluorene organic semiconductor material, preparation method and use thereof | |
| CN102653587B (en) | N,N'-di-substituted isoindigo and 2,7-carbazole copolymer and preparation method and application thereof | |
| CN103159920A (en) | Anthraquinone based co-polymer solar cell material, and preparation method and application thereof | |
| CN103159915A (en) | Isoindigo based co-polymer, and preparation method and application thereof | |
| CN102206328A (en) | Porphyrin copolymer containing benzothiadiazole unit, 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 | |
| CN103012748A (en) | N, N'-disubstituted isoindigo and p-divinylbenzene copolymer, and preparation method and application thereof | |
| CN103936965B (en) | Containing di-thiophene-benzo two (diazosulfide) multipolymer and its preparation method and application | |
| CN103772660A (en) | Copolymer containing cyclopentadiene bithiophene-benzo-bis (benzothiadiazole) copolymer and preparation method and application thereof | |
| CN103159936B (en) | Contain and polymkeric substance of thiazole unit and preparation method thereof and solar cell device | |
| CN115594828A (en) | Halogenated cyclopentadithiophene polymer, preparation method thereof and application thereof in photovoltaic devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |