CN102816305A - Bithiophene silicon pentalene-fluoroquinoxaline conjugated polymer - Google Patents

Bithiophene silicon pentalene-fluoroquinoxaline conjugated polymer Download PDF

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CN102816305A
CN102816305A CN2012103161650A CN201210316165A CN102816305A CN 102816305 A CN102816305 A CN 102816305A CN 2012103161650 A CN2012103161650 A CN 2012103161650A CN 201210316165 A CN201210316165 A CN 201210316165A CN 102816305 A CN102816305 A CN 102816305A
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fluoro
silicon
polymer
thieno
quinoxaline
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CN102816305B (en
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高潮
王维平
武海梅
刘红利
弥育华
安忠维
刘建群
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Xian Modern Chemistry Research Institute
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Abstract

The invention relates to a bithiophene silicon pentalene-fluoroquinoxaline conjugated polymer which has a general structural formula shown as a formula I. The polymer is prepared by subjecting bithiophene silicon pentalene monomer serving as an electron supply unit and bibromide substituted fluoroquinoxaline monomer serving as an electron receiving unit to Stille coupling reaction and donor materials of polymer bulk heterojunction solar cells. Strong electron drawing group fluorine atoms are introduced on an electron deficiency quinoxaline, so that HOMO energy level of materials can be effectively lowered to increase open-circuit voltage of polymer photovoltaic cells.

Description

Two thieno-ring silicon pentadienes-fluoro quinoxaline conjugated polymers
Technical field
The invention belongs to filed of functional, be specifically related to a kind of pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers.
Background technology
Sun power is one of energy the most likely in future, is a kind of inexhaustible, nexhaustible pollution-free clear energy sources.From 1954; Since first silicon solar cell succeeded in developing; Various forms of solar cells are come out one after another, and research and most widely used solar cell mainly are silicon single crystal, polysilicon and non-crystalline silicon series battery at present, yet the silion cell raw materials cost is high; Complex manufacturing has limited the more widely-used of it.Polymer solar battery have low cost, flexible good, be prone to significantly advantage such as preparation, the modification through material can improve Solar cell performance effectively.Therefore, this type solar cell has important development and application prospect, becomes the forward position and the emphasis of present polymer photovoltaic cell research.At present, still there is the problem of efficiency of conversion in polymer battery.Developing efficiently, conjugated polymers improves the focus that its photovoltaic energy conversion efficient is the present research in this field to body and acceptor material.With regard to donor material; In order to obtain the polymer materials of superperformance, electron rich unit (D) and electron deficiency unit (A) giving of introducing alternately that the main chain of conjugated polymers forms-acceptor (D-A-D) type polymkeric substance is become the emphasis of giving the research of body polymkeric substance at present.
Recently, the investigator designs and has synthesized a kind ofly based on the giving-the receptor type multipolymer of quinoxaline, has efficiency of conversion preferably.Synthetic PECz-DTQX such as Cao Yong reaches 6.07%, [Adv.Mater.2011,23 (27), 3086-3089] with the photoelectric transformation efficiency of PCBM blend.Fluorine atom has stronger electrophilic characteristic, often is introduced in the material short of electricity unit, reduces the HOMO energy level of donor material.The HOMO energy level of synthetic polymer PTB5 such as Yu Luping is-5.01ev; The HOMO energy level of introducing fluorine atom post polymerization thing is reduced to-5.12ev, and its open circuit voltage has promoted 0.08V, [L.Yu; Et al.J.Am.Chem.Soc.2009; 131,7792-7799], the characteristic electron that draws of fluorine atom well embodies.Fluorine atom is to effect of material performance in view of the above; On this short of electricity of quinoxaline unit, introduce fluorine atom; Prepare novel fluorine-containing giving-receptor type polymkeric substance and be expected to reduce the HOMO ability; Promote open circuit voltage, further improve the device photovoltaic performance, but the preparation of relevant this type of material and be applied to also not see so far in the polymer photovoltaic cell research and report.
Summary of the invention
To defective or deficiency that prior art exists, one object of the present invention is, a kind of pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers is provided, to satisfy the needs of polymer photovoltaic cell photoactive layers electron donor material.
Another object of the present invention is; With the novel two thieno-ring silicon pentadienes-fluoro quinoxaline conjugated polymers that obtains; Be used to prepare the application of polymer photovoltaic cell; Utilize the characteristic electron that draws of fluorine atom, reduce the HOMO energy level of polymer materials, and then promote the open circuit voltage of polymer photovoltaic cell.
To achieve these goals, a kind of pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers disclosed by the invention is characterized in that its general structure is suc as formula shown in the I:
Figure GDA00002080368300021
In the formula, R 1=H or F; R 2Be: a position or para-position carbon atomicity are the alkoxyl phenyl of 4 to 20 straight or branched; Or: carbonatoms is the 2-alkylthrophene base or 2 of 4 to 20 straight or branched, 3-dialkyl group thienyl.
The present invention provides a kind of preferred pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers A, and its structure is suc as formula shown in the II:
Figure GDA00002080368300031
The present invention provides another kind of preferred two thieno-ring silicon pentadienes-fluoro quinoxaline conjugated polymers B, and its structure is suc as formula shown in the III:
Figure GDA00002080368300032
The present invention provides another preferred two thieno-ring silicon pentadienes-fluoro quinoxaline conjugated polymers C, and its structure is suc as formula shown in the IV:
Figure GDA00002080368300033
The present invention provides another preferred two thieno-ring silicon pentadienes-fluoro quinoxaline conjugated polymers D, and its structure is suc as formula shown in the V:
Figure GDA00002080368300041
The present invention also provides a kind of preferred pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers E, and its structure is suc as formula shown in the VI:
Figure GDA00002080368300042
The present invention also provides another kind of preferred two thieno-ring silicon pentadienes-fluoro quinoxaline conjugated polymers F, and its structure is suc as formula shown in the VII:
Figure GDA00002080368300043
Above-mentioned pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers, its polyreaction adopt the reaction equation shown in Scheme 1 to carry out.
Figure GDA00002080368300051
Concrete synthesis step is following:
(1) preparation of fluorine-containing quinoxaline in short of electricity unit and verivate thereof
With 5 or 5,6 fluorine-containing 4,7-two bromo-2,1; The 3-diazosulfide is dissolved in the absolute ethyl alcohol, adds Peng Qinghuana under 0 ℃ in batches, reacts 20h under the room temperature then, and reaction finishes to concentrate removes ethanol; Add suitable quantity of water, ethyl acetate extraction, organic phase is used anhydrous magnesium sulfate drying; Bullion silicagel column purifying obtains fluorinated diamine, then with 1, and 2-two R 2Base second diketone is a solvent reaction with acetic acid, make 6 or 6,7 fluorine-containing 5,8-two bromo-2,3-two R 2The base quinoxaline.
(2) preparation of two thieno-ring silicon pentadienes-fluoro quinoxaline conjugated polymers
This is reflected under the nitrogen protection and carries out, and will receive body unit 6 or 6,7 fluorine-containing 5,8-two bromo-2,3-two R 2The molar weight of base quinoxaline is as 2 of matching criterion and equimolar amount, two (tin trimethyl)-4 of 6-; 4-diisooctyl-4-silicon-two thieno-ring silicon pentadienes joins in two mouthfuls of flasks of exsiccant, the toluene dissolving; Fluoro quinoxaline monomer concentration is controlled at about 0.03mol/L, adds catalyzer three (diphenylmethylene acetone) two palladiums of 0.02 times of molar weight and the part tri-o-tolyl phosphorus of 0.08 times of molar weight behind the ventilation 0.5h, continues ventilation 0.5h; Begin heating then, behind the back flow reaction 48h, stopped reaction; System is cooled to room temperature, and reaction solution is splashed into sedimentation in the methyl alcohol, filters; 50 ℃ of bakings of the polymkeric substance vacuum drying oven of collecting 12h carries out cable-styled extraction with methyl alcohol, normal hexane, chloroform successively, concentrates chloroform extracted solution; With methyl alcohol sedimentation once more, filter, obtain suc as formula a kind of pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers that contain shown in the I.
Beneficial effect of the present invention is; Fluorine atom is incorporated on the phenyl ring of electron deficiency unit quinoxaline,, reduces the HOMO energy level of polymer materials owing to the electrical characteristic of haling of fluorine atom; Thereby open circuit voltage that can boost device; Adopt fluorine-containing quinoxaline derivatives as the short of electricity unit, 2, two (tin trimethyl)-4 of 6-; 4-diisooctyl-4-silicon-two thieno-ring silicon pentadienes have prepared a kind of pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers as giving electric unit through the Stille linked reaction.Utilize cyclic voltammetry; With the two thieno-ring silicon pentadienes of fluoro not-quinoxaline conjugated polymers (structural formula A ' ~ C '; Referring to table 1) compare; The HOMO energy level of single fluoropolymer is the low 0.02-0.2eV of fluoric more not, and the HOMO of two fluorinated polymers is the low 0.05～0.3eV of fluoric more not.Above-mentioned fluoro material and PCBM blended applications are in the body heterojunction optical activity layer of polymer solar cell, and the open circuit voltage of device is at 0.6～1.0V.
Description of drawings
Fig. 1 is a polymer A ' C-V figure.
Fig. 2 is the C-V figure of polymer A.
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed description.
Embodiment
Be the embodiment that the contriver provides below, set forth the synthetic and performance of polymkeric substance respectively in detail, just in order to understand the present invention better.The invention is not restricted to these embodiment.
Embodiment 1:
Short of electricity unit 6-fluoro-5,8-two bromo-2,3-two (3-octyloxyphenyl) quinoxaline synthetic:
(1) the 4-fluoro-3,6-two bromo-1, the preparation of 2-phenylenediamine (compound 2)
Carry out according to reaction equation as follows:
Figure GDA00002080368300071
5-fluoro-4,7-two bromo-2,1, (5g 0.016mol) is dissolved in the 150ml absolute ethyl alcohol 3-diazosulfide, adds NaBH under 0 ℃ in batches 4(11.1g 0.29mol), reacts 20h under the room temperature then.After reaction finishes, concentrate and remove ethanol, add 160ml water, ethyl acetate extraction, saturated common salt water washing organic phase, last anhydrous MgSO 4Dry.Concentrate the thick product that obtains behind the removal organic solvent and use the silicagel column purifying, eluent is selected n-hexane/ethyl acetate for use, and (25:1 v/v), obtains 4-fluoro-3,6-two bromo-1,2-phenylenediamine 3.5g, productive rate 78%.
The preparation of (2) 1,2-two (3-octyloxyphenyl) second diketone (compound 5)
Carry out according to reaction equation as follows:
Figure GDA00002080368300072
To CuBr (4.33g, in THF solution 30.2mmol) (40ml) add LiBr (5.25g, 60.4mmol), stirring and dissolving under the room temperature; Temperature is reduced to 0 ℃ under the ice bath, begin to drip a Grignard reagent of bromobenzene octyl ether (a bromobenzene octyl ether (and 8.6g, 30.2mmol), Mg (1g; 41.7mmol), THF (30ml)), behind the reaction 20min, begin to drip oxalyl chloride (1.71g under 0 ℃; 13.5mmol), dropwise, continue reaction 30min.In system, add saturated NH 4Cl solution cancellation reaction, ethyl acetate extraction, saturated common salt water washing organic phase, anhydrous MgSO 4Drying obtains crude product after concentrate removing organic solvent, and silicagel column purifying, eluent are selected n-hexane/ethyl acetate for use (200:1 v/v), is obtained 1,2-two (3-octyloxyphenyl) second diketone.
(3) the 6-fluoro-5,8-two bromo-2, the preparation of 3-two (3-octyloxyphenyl) quinoxaline (compound 6)
Carry out according to reaction equation as follows:
Figure GDA00002080368300081
4-fluoro-3,6-two bromo-1, (0.59g, 1.9mmol) with 1, (0.88g 1.9mmol) is dissolved among the 40mlHAc 2-two (3-octyloxyphenyl) second diketone the 2-phenylenediamine, is warming up to 60 ℃, closes heating.React 2h under the room temperature.Suction filtration, the washing with alcohol filter cake gets 6-fluoro-5,8-two bromo-2,3-two (3-octyloxyphenyl) quinoxaline 1.31g, productive rate 97%.
The nuclear-magnetism characterization data: 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: short of electricity unit 6-fluoro-5,8-two bromo-2,3-two (4-octyloxyphenyl) quinoxaline (compound 8) synthetic
Carry out according to reaction equation as follows:
With 4-fluoro-3,6-two bromo-1,2-phenylenediamine and 1,2-two (4-octyloxyphenyl) second diketone is a raw material, according to the method for synthetic compound 6, obtains title product, productive rate 82% fully.
Embodiment 3:
Short of electricity unit 6,7-two fluoro-5,8-two bromo-2,3-two (3-octyloxyphenyl) quinoxaline synthetic
(1) 4,5-two fluoro-3,6-two bromo-1, the preparation of 2-phenylenediamine (compound 10)
Carry out according to reaction equation as follows:
Figure GDA00002080368300091
5,6-two fluoro-4,7-two bromo-2,1, (10g 0.031mol) is dissolved in the 300ml absolute ethyl alcohol 3-diazosulfide, adds NaBH under 0 ℃ in batches 4(22.2g 0.59mol), reacts 5h under the room temperature then.After reaction finishes, concentrate and remove ethanol, add 200ml water, ethyl acetate extraction, saturated common salt water washing organic phase, last anhydrous MgSO 4Dry.Concentrate the thick product that obtains and use the silicagel column purifying, eluent is selected n-hexane/ethyl acetate for use, and (20:1 v/v), obtains 4,5-two fluoro-3,6-two bromo-1,2-phenylenediamine 6.1g, productive rate 65%.
(2) 6,7-two fluoro-5,8-two bromo-2, the preparation of 3-two (3-octyloxyphenyl) quinoxaline (compound 11)
Carry out according to reaction equation as follows:
4,5-two fluoro-3,6-two bromo-1, (0.60g, 2.0mmol) with 1, (1g 2.1mmol) is dissolved among the 50ml HAc 2-two (3-octyloxyphenyl) second diketone the 2-phenylenediamine, is warming up to 60 ℃, closes heating, reacts 4h under the room temperature.Suction filtration, the absolute ethanol washing filter cake gets 6-fluoro-5,8-two bromo-2,3-two (3-octyloxyphenyl) quinoxaline 1.16g, productive rate 87%.
Embodiment 4:
Short of electricity unit 6,7-two fluoro-5,8-two bromo-2,3-two (4-octyloxyphenyl) quinoxaline (compound 12) synthetic
Carry out according to reaction equation as follows:
Figure GDA00002080368300101
With 4,5-two fluoro-3,6-two bromo-1,2-phenylenediamine and 1,2-two (4-octyloxyphenyl) second diketone is a raw material, according to the method for synthetic compound 11, obtains title product, productive rate 72% fully.
Embodiment 5:6-fluoro-5,8-two bromo-2,3-two (5-octyl group thiophene) quinoxaline (compound 14) synthetic
Carry out according to reaction equation as follows:
Figure GDA00002080368300102
1, and 2-two (5-octyl group thiophene) second diketone (3g, 6.7mmol) with 4-fluoro-3,6-two bromo-1; The 2-phenylenediamine (2.28g 8.04mmol) joins in the two-mouth bottle, acetic acid (150ml) dissolving, and 40 ℃ are reacted 15h down; Naturally cooling, suction filtration, filter cake is used ethyl alcohol recrystallization, obtains 6-fluoro-5; 8-two bromo-2,3-two (5-octyl group thiophene) quinoxaline 3.31g, productive rate 70%.
Embodiment 6:6,7-two fluoro-5,8-two (5-bromothiophene)-2,3-two (5-octyl group thiophene) quinoxaline (compound 15) synthetic
Carry out according to reaction equation as follows:
Figure GDA00002080368300111
With 4,5-two fluoro-3,6-two bromo-1,2-phenylenediamine and 1,2-two (5-octyl group thiophene) second diketone is a raw material, according to the method for synthetic compound 14, obtains title product, productive rate 70% fully.
The nuclear-magnetism characterization data: 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: give electric unit 2, and 6-two (tin trimethyl)-4,4-two (iso-octyl)-4-silicon-two thiophene [3,2-b, 2 ', 3 '-d] pentalane (compound 17) synthetic
Carry out according to reaction equation as follows:
Figure GDA00002080368300112
(1.44g 2.51mmol) is dissolved among the anhydrous THF of 20mL compound 16, places-78 ℃ of low temperature baths.Butyllithium (1.9mL, 2.9mol/L hexane solution) slowly is added drop-wise in the system.Continue to stir 30min at-78 ℃ after dripping off, then the 7mL trimethyltin chloride is joined in the system, remove the low temperature bath, system slowly rises to the room temperature continued and stirs 1h.Pour reaction mixture in water cancellation reaction.With ethyl acetate extraction twice, the difference water, saturated common salt water washing organic phase merges organic phase, adds anhydrous magnesium sulfate drying, filters, and concentrates organic phase, obtains light green oily matter 17 (1.78g, productive rate 95.6%).
Embodiment 8: the preparation of polymer A
Carry out according to reaction equation as follows:
Figure GDA00002080368300121
Be reflected under the argon shield and carry out, compound 6-fluoro-5,8-two bromo-2,3-two (3-octyloxyphenyl) quinoxaline (214.2mg) and 2; Two (tin trimethyl)-4 of 6-, 4-two (iso-octyl)-4-silicon-two thiophene [3,2-b, 2 '; 3 '-d] pentalane (218.4mg) is dissolved in the 10ml toluene, and logical argon gas 0.5h adds catalyzer three (diphenylmethylene acetone) two palladiums (5.5mg) and part triphenyl phosphorus (9.8mg), begins to heat behind the ventilation 1h; Back flow reaction 48h, system is naturally cooling at room temperature, dropwise adds to sedimentation in the methyl alcohol, filters; 50 ℃ of bakings of the polymkeric substance vacuum drying oven of collecting 12h, the polymkeric substance that obtains is used methyl alcohol, normal hexane, the cable-styled extraction of chloroform successively, concentrates chloroform extracted solution; Drip sedimentation to the methyl alcohol once more, obtain 239mg polymer A (seeing table 1), be the fibrous solid of grape; Productive rate 81%, number-average molecular weight 36541, distribution coefficient 2.21.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag +Electrode is a reference electrode, Bu 4NPF 6Making ionogen, in acetonitrile, is 0.56V through the initial oxidation current potential of cyclic voltammetry polymer A film; Polymer A ' the initial oxidation current potential be 0.51V; According to the calculation formula of HOMO energy level-(eV of 4.72+ initial oxidation current potential/V), the HOMO energy level that obtains polymer A is-5.28eV, than fluoric respective material A ' not-5.23eV; Low 0.05eV sees table 1 and accompanying drawing.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61The sandwich battery structure of BM/LiF/Al is with polymer A and PC 61BM processes polymer photovoltaic cell according to weight ratio 1:2, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.72V, photoelectric transformation efficiency is 4.61%.
Embodiment 9: the polymer B preparation
Carry out according to reaction equation as follows:
With embodiment 8, just with 6-fluoro-5,8-two bromo-2; 3-two (3-octyloxyphenyl) quinoxaline changes 6 into, 7-two fluoro-5,8-two bromo-2; 3-two (3-octyloxyphenyl) quinoxaline adopts identical method to obtain the polymkeric substance that structural formula is B (seeing table 1), productive rate 77%; Number-average molecular weight is 24674, distribution coefficient 2.31.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag +Electrode is a reference electrode, Bu 4NPF 6Make ionogen, in acetonitrile, can be-5.32eV through the HOMO of cyclic voltammetry polymer B film, than fluoric respective material A ' not-5.23eV, low 0.09eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61The sandwich battery structure of BM/LiF/Al, with polymer B according to certain weight ratio and acceptor material PC 61BM processes polymer photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.75V, photoelectric transformation efficiency is 4.55%.
Embodiment 10: polymkeric substance C preparation
Carry out according to reaction equation as follows:
With embodiment 8, just with 6-fluoro-5,8-two bromo-2; 3-two (3-octyloxyphenyl) quinoxaline changes 6-fluoro-5 into, 8-two bromo-2,3-two (4-octyloxyphenyl) quinoxaline; Adopt identical method to obtain the polymkeric substance that structural formula is C (seeing table 1); Productive rate 78%, number-average molecular weight 31254, distribution coefficient 1.89.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag +Electrode is a reference electrode, Bu 4NPF 6Make ionogen, in acetonitrile, can be-5.26eV through the HOMO of cyclic voltammetry polymkeric substance C film, than fluoric respective material B ' not-5.20eV, low 0.06eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61The sandwich battery structure of BM/LiF/Al, with polymkeric substance C according to certain weight ratio and acceptor material PC 61BM processes polymer photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.71V, photoelectric transformation efficiency is 4.21%.
Embodiment 11: polymkeric substance D preparation
Carry out according to reaction equation as follows:
Figure GDA00002080368300151
With embodiment 8, just with 6-fluoro-5,8-two bromo-2; 3-two (3-octyloxyphenyl) quinoxaline changes 6 into, 7-two fluoro-5,8-two bromo-2; 3-two (3-octyloxyphenyl) quinoxaline adopts identical method to obtain the polymkeric substance that structural formula is D (seeing table 1), productive rate 82%; Number-average molecular weight 24561, distribution coefficient 1.78.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag +Electrode is a reference electrode, Bu 4NPF 6Make ionogen, in acetonitrile, can be-5.33eV through the HOMO of cyclic voltammetry polymkeric substance D film, than-5.20 of the B ' of fluoric respective material not, low 0.13eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61The sandwich battery structure of BM/LiF/Al, with polymkeric substance D according to certain weight ratio and acceptor material PC 61BM processes polymer photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.73V, photoelectric transformation efficiency is 4.39%.
Embodiment 12: polymkeric substance E preparation
Carry out according to reaction equation as follows:
Figure GDA00002080368300161
With embodiment 8, just with 6-fluoro-5,8-two bromo-2; 3-two (3-octyloxyphenyl) quinoxaline changes 6-fluoro-5 into, 8-two bromo-2,3-two (5-octyl group thiophene) quinoxaline; Adopt identical method to obtain the polymkeric substance that structural formula is E (seeing table 1); Productive rate 87%, number-average molecular weight 45781, distribution coefficient 2.11.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag +Electrode is a reference electrode, Bu 4NPF 6Make ionogen, in acetonitrile, can be-5.31eV through the HOMO of cyclic voltammetry polymkeric substance E film, than fluoric respective material C ' not-5.26eV, low 0.05eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61The sandwich battery structure of BM/LiF/Al, with polymkeric substance E according to certain weight ratio and acceptor material PC 61BM processes polymer photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.70V, photoelectric transformation efficiency is 3.56%.
Embodiment 13: polymkeric substance F preparation
Carry out according to reaction equation as follows:
Figure GDA00002080368300171
With embodiment 8, just with 6-fluoro-2,3-two (3-octyloxyphenyl) quinoxaline changes 6 into; 7-two fluoro-5,8-two bromo-2,3-two (5-octyl group thiophene) quinoxaline; Adopt identical method to obtain the polymkeric substance that structural formula is F (seeing table 1); Productive rate 80%, number-average molecular weight 33456, distribution coefficient 2.07.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag +Electrode is a reference electrode, Bu 4NPF 6Make ionogen, in acetonitrile, can be-5.39eV through the HOMO of cyclic voltammetry polymkeric substance F film, than fluoric respective material C ' not-5.26eV, low 0.13eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61The sandwich battery structure of BM/LiF/Al, with polymkeric substance F according to certain weight ratio and acceptor material PC 61BM processes polymer photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.72V, photoelectric transformation efficiency is 3.78%.
The HOMO energy level of table 1 polymkeric substance
Figure GDA00002080368300172
Figure GDA00002080368300181

Claims (8)

1. two thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers is characterized in that general structure is suc as formula shown in the I:
Figure FDA00002080368200011
In the formula, R 1Be H or F atom; R 2Be: a position or para-position carbon atomicity are the alkoxyl phenyl of 4 to 20 straight or branched; Or: carbonatoms is the 2-alkylthrophene base or 2 of 4 to 20 straight or branched, 3-dialkyl group thienyl.
2. as claimed in claim 1 pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers is characterized in that structure is suc as formula shown in the II:
Figure FDA00002080368200012
3. as claimed in claim 1 pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers is characterized in that structure is suc as formula shown in the III:
Figure FDA00002080368200021
4. as claimed in claim 1 pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers is characterized in that structure is suc as formula shown in the IV:
Figure FDA00002080368200022
5. as claimed in claim 1 pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers is characterized in that structure is suc as formula shown in the V:
Figure FDA00002080368200023
6. as claimed in claim 1 pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers is characterized in that structure is suc as formula shown in the VI:
Figure FDA00002080368200031
7. as claimed in claim 1 pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers is characterized in that structure is suc as formula shown in the VII:
Figure FDA00002080368200032
8. one of them described pair of thieno-ring silicon pentadiene-fluoro quinoxaline conjugated polymers of claim 1 to 7, the application that is used to prepare polymer photovoltaic cell.
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CN102206329A (en) * 2010-03-31 2011-10-05 海洋王照明科技股份有限公司 Dithiophene silole-quinoxalines conjugated polymer, and its preparation method and application

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