CN102827357B - Two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers - Google Patents

Two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers Download PDF

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CN102827357B
CN102827357B CN201210316919.2A CN201210316919A CN102827357B CN 102827357 B CN102827357 B CN 102827357B CN 201210316919 A CN201210316919 A CN 201210316919A CN 102827357 B CN102827357 B CN 102827357B
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bis
fluoro
thieno
cyclopentadiene
polymkeric substance
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CN102827357A (en
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高潮
王维平
武海梅
陈键
陈冬
安忠维
丛志远
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Xian Modern Chemistry Research Institute
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Abstract

The object of the invention is to the electrophilic characteristic utilizing fluorine atom, develop a kind of novel D-A-D type donor polymer material containing fluoroquinoxaline, reduce the HOMO energy level of polymer materials.The invention discloses a kind of two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers, general structure is as follows: in formula, R 1h or F atom; R 2between being, position or para-position carbon atomicity are the alkoxyl phenyl of the straight or branched of 4 to 20, or carbonatoms is 2-alkylthrophene base or 2, the 3-dialkylthiophene base of the straight or branched of 4 to 20.The present invention by comparing with the polymer phase of corresponding non-fluoro, the low 0.02 ~ 0.2eV of polymkeric substance of the more non-fluoro of HOMO energy level of single fluoropolymer, the low 0.05 ~ 0.3eV of polymkeric substance of the more non-fluoro of HOMO energy level of two fluorinated polymer.

Description

Two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers
Technical field
The invention belongs to filed of functional, be specifically related to a kind of two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers.
Background technology
Energy problem is the matter of utmost importance of countries in the world Economic development now, and sun power is directly converted to electric energy and heat energy brings benefit to the mankind is pursuing a goal of scientist always.One of effective way of developing low-cost solar cell is started with from material exactly, effectively can be improved the performance of solar cell by the modification of material.Polymer solar battery has the significantly advantage such as low cost, flexible, easy preparation, and therefore, this kind of solar cell has important development and application prospect, becomes forward position and the emphasis of the research of current photovoltaic cell.At present, still there is the not high problem of efficiency of conversion in polymer battery.Developing efficient conjugated polymers to body and acceptor material is the focus that this field is studied at present to improve its photovoltaic energy conversion efficiency.With regard to donor material, in order to obtain the polymer materials of superperformance, what main chain electron rich unit (D) and electron deficiency unit (A) alternately being introduced conjugated polymers was formed becomes the emphasis that current donor polymer is studied to-acceptor (D-A-D) type polymkeric substance.
Recently, people's design and synthesis is a kind of based on the giving of quinoxaline-by precursor copolymer, has a good efficiency of conversion.Cao Yong etc. synthesize PECz-DTQX, and the photoelectric transformation efficiency after blended with PCBM reaches 6.07%, [Adv.Mater.2011,23 (27), 3086-3089].The electrophilic characteristic of fluorine atom is often introduced in material short of electricity unit, reduces the HOMO energy level of donor material.The HOMO energy level of the synthetic polymer PTB5 such as Yu Luping is-5.01ev, and the HOMO energy level introducing fluorine atom post-consumer polymer is reduced to-5.12ev, and its open circuit voltage improves 0.08V, [L.Yu, et al.J.Am.Chem.Soc.2009,131,7792-7799].In view of above-mentioned fluorine atom is on the impact of material property, this electron deficiency of quinoxaline unit is introduced fluorine atom prepare novel fluorine-containing to-receptor type polymkeric substance be expected to reduce further HOMO can, promote open circuit voltage, thus improve device photovoltaic performance.But the preparation that yet there are no so far about this type of material and the report that is applied in photovoltaic cell thereof.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to develop a kind of novel D-A-D type donor polymer material containing fluoroquinoxaline, meet the needs of polymer photovoltaic cell photoactive layers electron donor material.
Another object of the present invention is the electrophilic characteristic utilizing fluorine atom, reduces the HOMO energy level of polymer materials, and then promotes the open circuit voltage of photovoltaic cell.
In order to realize above-mentioned technical assignment, the present invention adopts following technical scheme to be achieved:
A kind of two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers, its general structure is such as formula shown in I:
In formula, R 1h or F atom; R 2between being, position or para-position carbon atomicity are the alkoxyl phenyl of the straight or branched of 4 to 20, or carbonatoms is 2-alkylthrophene base or 2, the 3-dialkylthiophene base of the straight or branched of 4 to 20.
The present invention also has following technical characterstic:
The structure of described two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymerss is such as formula shown in II:
The structure of described two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymerss is such as formula shown in III:
The structure of described two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymerss is such as formula shown in IV:
The structure of described two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymerss is such as formula shown in V:
The structure of described two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymerss is such as formula shown in VI:
The structure of described two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymerss is such as formula shown in VII:
Described two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymerss are for the preparation of the application of polymer photovoltaic cell.
To achieve these goals, disclosed by the invention pair of thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers, carries out according to reaction mechanism as follows:
Concrete synthesis step is as follows:
(1) preparation of the fluorine-containing quinoxaline of short of electricity unit and derivative thereof
By 5 or 5,6 fluorine-containing 4,7-bis-bromo-2,1,3-diazosulfide is dissolved in dehydrated alcohol, adds sodium borohydride at 0 DEG C in batches, then 20h is reacted under room temperature, reaction terminates rear distillation under vacuum and removes ethanol, adds suitable quantity of water, extraction into ethyl acetate, organic phase anhydrous magnesium sulfate drying, crude product obtains fluorinated diamine through purification by silica gel column chromatography, then with 1,2-bis-R 2base replaces second two reactive ketone, and obtained 6 or 6,7 fluorine-containing 5,8-bis-bromo-2,3-bis-R 2base quinoxaline.
(2) preparation of two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers
This reaction is carried out under nitrogen protection, will by fluorine-containing 5,8-bis-bromo-2,3-bis-R of body unit 6 or 6,7 2the molar weight of base quinoxaline is as matching criterion, with 2 of equimolar amount, the two tin trimethyl-4 of 6-, 4-diisooctyl-4-hydrogen-bis-thieno-cyclopentadiene, together join in two mouthfuls of dry flasks, toluene dissolves, fluoroquinoxaline monomer concentration controls at about 0.03mol/L, catalyzer three (dibenzylideneacetone) two palladium of 0.02 times of molar weight and the part tri-o-tolyl phosphorus of 0.08 times of molar weight is added after ventilation 0.5h, continue ventilation 0.5h, then heating is started, after back flow reaction 48h, stopped reaction, system is cooled to room temperature, reaction solution is instilled sedimentation in methyl alcohol, filter, the polymkeric substance vacuum drying oven 50 DEG C collected dries 12h, use methyl alcohol successively, normal hexane, chloroform carries out soxhlet extraction, concentrated chloroform extracted solution, with methyl alcohol sedimentation again, filter, obtain such as formula the two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymerss shown in I.
The present invention adopts fluorine-containing quinoxaline derivatives as short of electricity unit, two tin trimethyl-4, the 4-diisooctyl-4-hydrogen-bis-thieno-cyclopentadiene of 2,6-is as giving electric unit, two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers (see table 1, A ~ F) has been prepared by Stille linked reaction.Tested by Cyclic voltamogram, with the two thieno-cyclopentadiene-quinoxaline conjugated polymers of non-fluoro (see table 1, A ' ~ C ') compare, draw following result: the low 0.02-0.2eV of the more non-fluoro of HOMO energy level of single fluoropolymer, the HOMO of two fluorinated polymer can the low 0.05 ~ 0.3eV of more non-fluoro.Above-mentioned fluorinated polymer and PCBM blended applications are in body heterojunction optical activity layer of polymer solar cell, and the open circuit voltage of device is at 0.6 ~ 1.0V.
Accompanying drawing explanation
Fig. 1 be polymer A ' C-V figure.
Fig. 2 is the C-V figure of polymer A.
Below in conjunction with drawings and Examples, particular content of the present invention is described in more detail.
Embodiment
Below provide specific embodiments of the invention, it should be noted that the present invention is not limited to following specific embodiment, all equivalents done on technical scheme basis all fall into protection scope of the present invention.
Embodiment 1: the synthesis of short of electricity unit 6-fluoro-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline
(1) preparation of fluoro-3,6-bis-bromo-1, the 2-phenylenediamines (compound 2) of 4-
Fluoro-4,7-bis-bromo-2,1, the 3-diazosulfides (5g, 0.016mol) of 5-are dissolved in 150ml dehydrated alcohol, add NaBH at 0 DEG C in batches 4(11.1g, 0.29mol), then reacts 20h under room temperature.After reaction terminates, remove ethanol with distillation under vacuum, add 160ml water, extraction into ethyl acetate, saturated common salt water washing organic phase, last anhydrous MgSO 4dry.Concentrated removal organic solvent, the thick product n-hexane/ethyl acetate obtained (normal hexane is 25:1 with the volume ratio of ethyl acetate) silica gel column chromatography is separated, and obtains fluoro-3,6-bis-bromo-1, the 2-phenylenediamine 3.5g of 4-, productive rate 78%.
The preparation of (2) 1,2-bis-(3-octyloxyphenyl) second diketone (compound 5)
To CuBr (4.33g, in THF solution 30.2mmol), (40ml) adds LiBr (5.25g, 60.4mmol), stirred at ambient temperature dissolves, under ice bath, temperature is down to 0 DEG C, start a Grignard reagent (bromobenzene octyl ether (8.6g of bromobenzene octyl ether between dripping, 30.2mmol), Mg (1g, 41.7mmol), THF (30ml)), after reaction 20min, start at 0 DEG C to drip oxalyl chloride (1.71g, 13.5mmol), dropwise, continue reaction 30min.Saturated NH is added in system 4the cancellation of Cl solution is reacted, extraction into ethyl acetate, saturated common salt water washing organic phase, anhydrous MgSO 4drying, concentrated removal organic solvent, the crude product n-hexane/ethyl acetate obtained (volume ratio of normal hexane and ethyl acetate is 200:1) silica gel column chromatography, obtains 1,2-bis-(3-octyloxyphenyl) second diketone.
(3) preparation of fluoro-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline (compounds 6) of 6-
Fluoro-3,6-bis-bromo-1, the 2-phenylenediamines (0.59g, 1.9mmol) of 4-and 1,2-bis-(3-octyloxyphenyl) second diketone (0.88g, 1.9mmol) are dissolved in 40mlHAc, are warming up to 60 DEG C, close heating, react 2h under room temperature.Suction filtration, washing with alcohol filter cake, obtains 6-fluoro-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline 1.31g, productive rate 97%.
Nuclear-magnetism characterization data is: 1h NMR (500MHz, CDCl 3, ppm): δ=7.97 (d, 1H), 7.27 (m, 4H), 7.21 (t, 2H), 6.98 (m, 2H), 3.9 (t, 4H), 1.76 (m, 4H), 1.45 (dd, 4H), 1.34 (m, 16H), 0.93 (t, 6H).
Embodiment 2: the synthesis of fluoro-5,8-bis-bromo-2,3-bis-(4-octyloxyphenyl) quinoxaline (compounds 8) of short of electricity unit 6-
For raw material, completely according to the method for synthetic compound 6, target product is obtained, productive rate 82% with fluoro-3,6-bis-bromo-1, the 2-phenylenediamines of 4-and 1,2-bis-(4-octyloxyphenyl) second diketone.
Embodiment 3: the synthesis of short of electricity unit 6,7-bis-fluoro-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline
The preparation of fluoro-3,6-bis-bromo-1, the 2-phenylenediamines (compound 10) of (1) 4,5-bis-
Fluoro-4,7-bis-bromo-2,1, the 3-diazosulfides (10g, 0.031mol) of 5,6-bis-are dissolved in 300ml dehydrated alcohol, add NaBH at 0 DEG C in batches 4(22.2g, 0.59mol), then reacts 20h under room temperature.After reaction terminates, remove ethanol with distillation under vacuum, add 200ml water, extraction into ethyl acetate, saturated common salt water washing organic phase, last anhydrous MgSO 4dry.Concentrated thick product n-hexane/ethyl acetate (volume ratio of normal hexane and ethyl acetate the is 20:1) silica gel column chromatography obtained, obtains fluoro-3,6-bis-bromo-1, the 2-phenylenediamine 6.1g of 4,5-bis-, productive rate 65%.
The preparation of fluoro-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline (compounds 11) of (2) 6,7-bis-
Fluoro-3,6-bis-bromo-1, the 2-phenylenediamines (0.60g, 2.0mmol) of 4,5-bis-and 1,2-bis-(3-octyloxyphenyl) second diketone (1g, 2.1mmol) are dissolved in 50ml HAc, are warming up to 60 DEG C, close heating, react 4h under room temperature.Suction filtration, absolute ethanol washing filter cake, obtains 6,7-bis-fluoro-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline 1.16g, productive rate 87%.
Embodiment 4: the synthesis of fluoro-5,8-bis-bromo-2,3-bis-(4-octyloxyphenyl) quinoxaline (compounds 12) of short of electricity unit 6,7-bis-
For raw material, completely according to the method for synthetic compound 11, target product is obtained, productive rate 72% with fluoro-3,6-bis-bromo-1, the 2-phenylenediamines of 4,5-bis-and 1,2-bis-(4-octyloxyphenyl) second diketone.
The synthesis of fluoro-5,8-bis-bromo-2,3-bis-(5-octyl thiophene) quinoxaline (compounds 14) of embodiment 5:6-
1,2-bis-(5-octyl thiophene) second diketone (3g, 6.7mmol) and 4-fluoro-3, bromo-1, the 2-phenylenediamine (2.28g, 8.04mmol) of 6-bis-joins in two-mouth bottle, acetic acid (150ml) dissolves, and reacts 15h, naturally cooling at 40 DEG C, suction filtration, filter cake ethyl alcohol recrystallization, obtains 6-fluoro-5,8-bis-bromo-2,3-bis-(5-octyl thiophene) quinoxaline 3.31g, productive rate 70%.
The synthesis of embodiment 6:6,7-bis-fluoro-5,8-bis-(5-bromothiophene)-2,3-bis-(5-octyl thiophene) quinoxaline (compound 15)
For raw material, completely according to the method for synthetic compound 14, target product is obtained, productive rate 70% with fluoro-3,4-bis-bromo-1, the 2-phenylenediamines of 4,5-bis-and 1,2-bis-(5-octyl thiophene) second diketone.Nuclear-magnetism characterization data is: 1h NMR (CDCl 3, 500MHz, ppm), δ, 7.52 (dd, 2H), 6.81 (d, 2H), 2.93 (t, 4H), 1.78 (m, 4H), 1.46 (dd, 4H), 1.35-1.30 (m, 16H), 0.95 (t, 6H).
Embodiment 7: to the synthesis of two (iso-octyl)-4-hydrogen two thiophene [3,2-b, 2 ', 3 '-d] pentalene (compound 17) of electric unit 2,6-two (tin trimethyl)-4,4-
Compound 16 (1.40g, 2.5mmol) is dissolved in the anhydrous THF of 20ml, is placed in-78 DEG C of low temperature baths.Under Ar protection, butyllithium (1.9ml, 2.9mol/L hexane solution) is slowly added drop-wise in system.Continue to stir 30min at-78 DEG C after dripping off, then join in system by 7ml trimethyltin chloride, remove low temperature bath, system continues to stir 1h after slowly rising to room temperature.Reaction mixture is poured into water cancellation reaction.Be extracted with ethyl acetate twice, use water respectively, saturated common salt water washing organic phase, merge organic phase, add anhydrous magnesium sulfate drying, filter, concentrated organic phase, obtains product 17 (1.67g, productive rate 91%).
Embodiment 8: polymer A
Reaction is carried out under nitrogen protection, compound 6-fluoro-5, 8-bis-bromo-2, 3-bis-(3-octyloxyphenyl) quinoxaline (214.2mg) and 2, two (tin trimethyl)-4 of 6-, two (iso-octyl)-4-hydrogen-two thiophene [3 of 4-, 2-b, 2 ', 3 '-d] and pentane (218.4mg) is dissolved in 10ml toluene, logical nitrogen 0.5h, add catalyzer three (dibenzylideneacetone) two palladium (5.5mg) and part triphenyl phosphorus (9.8mg), heating is started after continuing ventilation 0.5h, back flow reaction 48h, system is naturally cooling at room temperature, dropwise add to sedimentation in methyl alcohol, filter, the polymkeric substance obtained uses methyl alcohol successively, normal hexane, chloroform soxhlet extraction, concentrated chloroform extracted solution, again drop to sedimentation in methyl alcohol, obtain polymer A 239mg, for intense violet color fibrous solids, productive rate 81%, number-average molecular weight 23412, distribution coefficient 2.63.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, and Ag/Ag+ electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile, through the initial oxidation current potential of cyclic voltammetry polymer A film for 0.53V, polymer A ' initial oxidation current potential for 0.48V, according to calculation formula-(4.72+ initial oxidation current potential/V) eV of HOMO energy level, the HOMO energy level obtaining polymer A film is-5.25eV, and than-the 5.20eV of the respective material A ' of non-fluoro, low 0.05eV, in table 1 and accompanying drawing.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, by polymer A and PC 61bM makes photovoltaic cell according to weight ratio 1:2, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source to show to gather, open circuit voltage is 0.73V, and short-circuit current density is 10.31mA/cm 2, packing factor is 60.9%, and photoelectric transformation efficiency is 4.61%.
Embodiment 9: polymer B
With embodiment 8, just by fluoro-for 6-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline changes 6-fluoro-5,8-bis-bromo-2,3-bis-(4-octyloxyphenyl) quinoxaline into, adopt identical method to obtain polymkeric substance that structural formula is B, productive rate 87%, number-average molecular weight 38652, distribution coefficient 1.67.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, and Ag/Ag+ electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile, can be-5.23eV through the HOMO of cyclic voltammetry polymer B film, than-the 5.16eV of the respective material B ' of non-fluoro, low 0.07eV, in table 1.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, by polymer B according to certain weight ratio and acceptor material PC 61bM makes photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source to show to gather, open circuit voltage is 0.70V, and photoelectric transformation efficiency is 3.56%.
Embodiment 10: polymkeric substance C
With embodiment 8, just by fluoro-for 6-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline changes 6-fluoro-5,8-bis-bromo-2,3-bis-(5-octyl thiophene) quinoxaline into, adopt identical method to obtain polymkeric substance that structural formula is C, productive rate 73%, number-average molecular weight 27385, distribution coefficient 1.87.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, and Ag/Ag+ electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile, can be-5.26eV through the HOMO of cyclic voltammetry polymkeric substance C film, than-the 5.22eV of the respective material C ' of non-fluoro, low 0.04eV, in table 1.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, by polymkeric substance C according to certain weight ratio and acceptor material PC 61bM makes photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source to show to gather, open circuit voltage is 0.81V, and photoelectric transformation efficiency is 4.88%.
Embodiment 11: polymkeric substance D
With embodiment 8, just by fluoro-for 6-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline changes 6,7-bis-fluoro-5 into, 8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline, adopt identical method to obtain polymkeric substance that structural formula is D, productive rate 74%, number-average molecular weight 52318, distribution coefficient 2.02.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, and Ag/Ag+ electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile, can be-5.34eV through the HOMO of cyclic voltammetry polymkeric substance D film, than-the 5.20eV of the respective material A ' of non-fluoro, low 0.14eV, in table 1.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, by polymkeric substance D according to certain weight ratio and acceptor material PC 61bM makes photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source to show to gather, open circuit voltage is 0.74V, and photoelectric transformation efficiency is 4.28%.
Embodiment 12: polymkeric substance E
With embodiment 8, just by fluoro-for 6-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline changes 6,7-bis-fluoro-5 into, 8-bis-bromo-2,3-bis-(4-octyloxyphenyl) quinoxaline, adopt identical method to obtain polymkeric substance that structural formula is E, productive rate 76%, number-average molecular weight 43657, distribution coefficient 2.31.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, and Ag/Ag+ electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile, can be-5.42eV through the HOMO of cyclic voltammetry polymkeric substance E film, than-the 5.26eV of the respective material B ' of non-fluoro, low 0.16eV, in table 1.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, by polymkeric substance E according to certain weight ratio and acceptor material PC 61bM makes photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source to show to gather, open circuit voltage is 0.71V, and photoelectric transformation efficiency is 3.79%.
Embodiment 13: polymkeric substance F
With embodiment 8, just by fluoro-for 6-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline changes 6-fluoro-5,8-bis-bromo-2,3-bis-(5-octyl thiophene) quinoxaline into, adopt identical method to obtain polymkeric substance that structural formula is F, productive rate 71%, number-average molecular weight 52548, distribution coefficient 2.34
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, and Ag/Ag+ electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile, can be-5.47eV through the HOMO of cyclic voltammetry polymkeric substance F film, than-the 5.32eV of the respective material C ' of non-fluoro, low 0.15eV, in table 1.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, by polymkeric substance F according to certain weight ratio and acceptor material PC 61bM makes photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithle y2611 source tables gather, and open circuit voltage is 0.73V, and photoelectric transformation efficiency is 3.79%.
The HOMO energy level of table 1 polymkeric substance

Claims (3)

1. two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers, it is characterized in that, general structure is such as formula shown in I:
In formula, R 22-alkylthrophene base or 2, the 3-dialkylthiophene base of to be carbonatoms the be straight or branched of 4 to 20.
2. two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers as claimed in claim 1, it is characterized in that, the structure of described two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymerss is such as formula shown in IV:
3. the two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymerss as described in claim arbitrary in claim 1 to 2 are for the preparation of the application of polymer photovoltaic cell.
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