CN102816299B - Conjugated polymer of 4, 8-diisooctyl alkoxy phenyl [1, 2-b; 3, 4-b] bithiophene and fluoro-quinoxaline - Google Patents
Conjugated polymer of 4, 8-diisooctyl alkoxy phenyl [1, 2-b; 3, 4-b] bithiophene and fluoro-quinoxaline Download PDFInfo
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- CN102816299B CN102816299B CN201210316139.8A CN201210316139A CN102816299B CN 102816299 B CN102816299 B CN 102816299B CN 201210316139 A CN201210316139 A CN 201210316139A CN 102816299 B CN102816299 B CN 102816299B
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Abstract
The invention belongs to the field of functional polymer materials and particularly relates to a conjugated polymer of 4, 8-diisooctyl alkoxy phenyl [1, 2-b; 4, 5-b] bithiophene and fluoro-quinoxaline. The conjugated polymer is represented as formula I, is prepared by means of Stille coupled reaction of dibromo-fluoro-quinoxaline and 2, 6-bis (trimethyltin)-4, 8-diisooctyl alkoxy phenyl [1, 2-b; 4, 5-b] bithiophene and is used for electron donor materials of polymer bulk heterojunction photovoltaic cells. Fluorine atoms with strong electron withdrawing groups are introduced onto quinoxaline of an electron-deficient unit of the polymer, so that the HOMO (highest occupied molecular orbital) energy level of the materials can be effectively reduced, and further, open-circuit voltage of polymer photovoltaic cells is increased.
Description
Technical field
The invention belongs to filed of functional, be specifically related to the conjugated polymers of a kind of 4,8-, bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline and the application for the preparation of polymer photovoltaic cell thereof.
Background technology
Along with the growth of expanding economy and population, energy dilemma is increasingly sharpened, and develops reproducible new forms of energy and just becomes more and more urgent.
Sun power is as the inexhaustible green energy resource of one, and it utilizes, develops the extensive concern that has been subject to international community.Polymer solar battery because its preparation process is simple, cost is low, lightweight and can be prepared into the outstanding advantages such as flexible device, become in recent years domestic and international study hotspot, the focus of current polymer solar battery research is that the efficient conjugated polymers of exploitation improves its photovoltaic energy conversion efficiency to body and acceptor material.
For serving as the polymer materials of electron donor(ED), the absorption spectrum of material has determined the short-circuit current of device, and the HOMO energy level of material has determined the open circuit voltage of device, and the structure of material and carrier mobility have determined the packing factor of device.Well behaved to body polymer materials in order to obtain, what electron rich unit (D) and electron deficiency unit (A) were alternately introduced to the main chain of conjugated polymers forms becomes the emphasis to the research of body polymkeric substance at present to-acceptor (D-A-D) type polymkeric substance.
Quinoxaline and derivative thereof are as the novel short of electricity unit of a class, receive much concern in recent years and obtain good performance, the synthetic PECz-DTQX such as such as Cao Yong, reach 6.07% with the photoelectric transformation efficiency of PCBM blend, [advanced material Adv.Mater.2011,23 (27), 3086-3089].
Since 2009, fluorine atom, because volume is little, has again strong electrophilic characteristic and is introduced in short of electricity unit, by reducing the HOMO energy level of donor material and then the photoelectric transformation efficiency of boost device.The HOMO energy level of the synthetic PTB5 of the people such as such as Yu Luping be-5.01ev, the be reduced to-5.12ev of HOMO energy level of PTB4 after introducing fluorine atom, and open circuit voltage rises to 0.74V by 0.66V, [JACS J.Am.Chem.Soc.2009,131,7792-7799].In recent years this seminar has also done a large amount of work in this regard, and constantly has bibliographical information, for solid basis has been established in this research.In view of this field scientific research personnel's achievement in research, prepare novel fluorine-containing D-A-D type and be expected to obtain similar performance to body polymkeric substance if introduce fluorine atom on this electron deficiency of quinoxaline unit, but yet there are no so far about the preparation method of this type of material and be applied to the report in photovoltaic cell.
Summary of the invention
A technical problem to be solved by this invention is that the D-A-D type of fluoro quinoxaline of development of new, to body polymer materials, meets the needs of polymer photovoltaic cell photoactive layers electron donor material.
For this reason, provided by the invention 4, the conjugated polymers general structure of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline is as shown in formula I:
In formula I,
R
1for: H atom or F atom;
R
2for: a position or para-position carbon atomicity are the alkoxyl phenyl of 4 to 20 straight or branched, or for carbonatoms be 2-alkylthrophene base or 2, the 3-dialkyl group thienyl of 4 to 20 straight or branched.
Preferably (one), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline is as shown in formula II:
Preferably (two), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline is as shown in formula III:
Preferably (three), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline is as shown in (IV):
Preferably (four), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline is suc as formula shown in (V):
Preferably (five), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline is as shown in formula VI:
Preferably (six), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline is suc as formula shown in (VII):
It is above-mentioned 4 that another problem to be solved by this invention is to provide, and the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline is for the preparation of the application of polymer photovoltaic cell.Thereby 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 photovoltaic cell.
Disclosed by the invention a kind of 4, the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline, according to as shown in Scheme.1 polyreaction course carry out:
Concrete synthesis step is as follows:
(1) preparation of the fluorine-containing quinoxaline in 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 under room temperature, react 20h, reaction finishes to concentrate removes ethanol, adds suitable quantity of water, ethyl acetate extraction, organic phase anhydrous magnesium sulfate drying, crude product purification by silica gel column chromatography obtains fluorinated diamine, then with 1,2-, bis-R
2base second diketone is taking acetic acid as solvent reaction, make 6 or 6,7 fluorine-containing 5,8-bis-is bromo-2,3-bis-R
2base quinoxaline.
(2) preparation of polymkeric substance
This reaction is carried out under nitrogen protection, gets a certain amount of 6 or 6,7 of body units of being subject to fluorine-containing 5, and 8-bis-is bromo-2,3-bis-R
2base quinoxaline, with 2 of equimolar amount, two (tin trimethyl)-4 of 6-, 8-bis-octane-iso oxygen base phenyl [1, 2-b:4, 5-b '] bithiophene compound, join in two mouthfuls of dry flasks, toluene dissolves, fluoro quinoxaline monomer concentration is controlled at 0.03mol/L left and right, after ventilation 0.5h, add 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, continue ventilation 0.5h, then start heating, after back flow reaction 24h, stopped reaction, system is cooled to room temperature, reaction solution is splashed into sedimentation in methyl alcohol, filter, the 50 DEG C of baking 12h of polymkeric substance vacuum drying oven that collect, use successively methyl alcohol, normal hexane, chloroform carries out soxhlet extraction, concentrated chloroform extracted solution, with methyl alcohol sedimentation again, filter, obtain as shown in I 4, 8-bis-octane-iso oxygen base phenyl [1, 2-b:4, 5-b '] conjugated polymers of bithiophene and fluoro quinoxaline.
Compared with prior art, the present invention adopts fluorine-containing quinoxaline and derivative thereof as short of electricity unit, 2 of symmetrical configuration, excellent property, two (tin trimethyl)-4 of 6-, 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophene is as giving electric unit, synthesized single fluoro and two fluoro 4,8-bis-octane-iso oxygen base phenyl [1 by give-acceptor copolymerization mode, 2-b:4,5-b '] conjugated polymers of bithiophene and fluoro quinoxaline.Pass through cyclic voltammetry, with fluoro 4 not, 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] conjugated polymers (structural formula A ', B ' and the C ' of bithiophene and quinoxaline, in table 1) compare, the HOMO energy level of single fluorinated polymer is the lower 0.02～0.2eV of fluoro, the lower 0.05-0.3eV of fluoro of two fluorinated polymer HOMO energy levels.Above-mentioned fluoro material 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.
Brief description of the drawings
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.
Fig. 1 be polymer A ' C-V figure;
Fig. 2 is the C-V figure of polymer A.
Embodiment
In order to understand better the present invention, and performance synthetic to this polymkeric substance is described in detail respectively below, and the cited case does not limit the scope of the invention.
Embodiment 1: polymer A
Step 1,6-is fluoro-5, and 8-bis-is bromo-2, the preparation of 3-bis-(3-octyloxyphenyl) quinoxaline
Synthetic route is as follows:
(1) 4-is fluoro-3, and 6-bis-is bromo-1, the preparation of 2-phenylenediamine
5-is fluoro-4, and 7-bis-is bromo-2,1, and 3-diazosulfide (5g, 0.016mol) is dissolved in 150ml dehydrated alcohol, adds NaBH at 0 DEG C in batches
4(11.1g, 0.29mol), then reacts 20h under room temperature; After reaction finishes, concentrate and remove ethanol, add 160ml water, ethyl acetate extraction, saturated common salt water washing organic phase, finally uses anhydrous MgSO
4dry; The concentrated organic solvent of removing, the thick product silicagel column column chromatography purification obtaining, eluent is selected n-hexane/ethyl acetate (volume ratio of normal hexane and ethyl acetate is 25:1), obtains 4-fluoro-3, and 6-bis-is bromo-1,2-phenylenediamine 3.5g, productive rate 78%.
The preparation of (2) 1,2-bis-(3-octyloxyphenyl) second diketone
To CuBr (4.33g, in THF solution (40ml) 30.2mmol), add LiBr (5.25g, 60.4mmol), stirring and dissolving under room temperature, under ice bath, temperature is down to 0 DEG C, start to drip new system between the Grignard reagent [bromobenzene octyl ether (8.6g of bromobenzene octyl ether, 30.2mmol), Mg (1g, 41.7mmol), THF (30ml)], after reaction 20min, start to drip oxalyl chloride (1.71g, 13.5mmol) at 0 DEG C, dropwise, continue to add saturated NH in the backward system of reaction 30min
4cl solution cancellation reaction, ethyl acetate extraction, saturated common salt water washing organic phase, anhydrous MgSO
4dry, the concentrated thick product purification by silica gel column chromatography obtaining after organic solvent of removing, eluent is selected n-hexane/ethyl acetate (volume ratio of normal hexane and ethyl acetate is 200:1), obtains 1,2-bis-(3-octyloxyphenyl) second diketone 3.46g, productive rate 55%.
(3) 6-is fluoro-5, and 8-bis-is bromo-2, the preparation of 3-bis-(3-octyloxy benzene) quinoxaline
4-is fluoro-3, and 6-bis-is bromo-1, and 2-phenylenediamine (0.59g, 1.9mmol) and 1,2-bis-(3-octyloxyphenyl) second diketone (0.88g, 1.9mmol) is dissolved in 40mlHAc, is warming up to 60 DEG C, closes heating, under room temperature, reacts 2h; Suction filtration, washing with alcohol filter cake, obtains 6-fluoro-5, and 8-bis-is bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline 1.31g, productive rate 97%; 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).
Step 2, two (tin trimethyl)-4 of preparation 2,6-, 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes
Synthetic route is as follows:
The preparation of (1) 4,8-, bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes
4,8-dihydro phenyl [1,2-b:4,5-b '] bithiophene-4,8-diketone (8.8g, 40mmol), zinc powder (5.72g, 88mmol), NaOH (24g), 120ml water adds in 250ml flask, after stirring and refluxing 1h, add the Tetrabutyl amonium bromide of bromo-iso-octane (30g, 120mmol) and catalytic amount, continue backflow 2h, the color of reactant is yellow or orange, if the color of system is redness or scarlet, then adds excessive zinc powder (2.6g, 40mmol), reaction backflow 6h; System is poured in cold water, extracted with diethyl ether, the anhydrous MgSO of organic phase
4dry; Concentrated solvent, ethyl alcohol recrystallization twice for crude product, obtains 4,8-, bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophene 18.5g, and productive rate is 83%.
Two (tin trimethyl)-4 of (2) 2,6-, the preparation of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes
Reaction is carried out under nitrogen protection, 4,8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophene (6.1g, 13.6mmol), 200mlTHF dissolves, be cooled to-80 DEG C, start to drip butyllithium (36.3mmol, 2.2M), dropwise, at-80 DEG C, react 1h, naturally rise to room temperature and continue reaction 1h, be again cooled to-80 DEG C, disposable trimethyltin chloride (the 8g that adds, THF (30ml) solution 40.4mmol), removes cryostat, and room temperature reaction spends the night; Reaction solution is poured in 200ml water, n-hexane extraction, saturated common salt water washing organic phase, anhydrous MgSO
4dry.Crude product dehydrated alcohol recrystallization, obtains two (tin trimethyl)-4 of 2,6-, 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes (6.15g, 7.96mmol), productive rate 58.3%.
1H?NMR(500MHz,CDCl
3,ppm)：δ＝7.52(s,2H),4.23(d,4H),1.79(m,2H),1.54-1.36(m,16H),1.06(t,6H),0.96(t,6H),0.40(s,18H)。
Step 3, preparation polymer A
Synthetic route is as follows:
Reaction is carried out under nitrogen protection, 6-fluoro-5, 8-bis-bromo-2, 3-bis-(3-octyloxyphenyl) quinoxaline (214.2mg, 0.3mmol) He 2, two (tin trimethyl)-4 of 6-, 8-bis-octane-iso oxygen base phenyl [1, 2-b:4, 5-b '] bithiophene (231.6mg, 0.3mmol) be dissolved in 10ml toluene, logical nitrogen 0.5h, add catalyzer three (diphenylmethylene acetone) two palladiums (5.5mg) and part tri-o-tolyl phosphorus (9.8mg), after ventilation 0.5h, start heating, back flow reaction 24h, system is naturally cooling at room temperature, dropwise add to sedimentation in methyl alcohol, filter, the polymkeric substance obtaining is used methyl alcohol successively, normal hexane, chloroform soxhlet extraction, concentrated chloroform extracted solution, again drop to sedimentation in methyl alcohol, obtain polymer A 246mg, for the fibrous solid of atropurpureus, productive rate 82%, number-average molecular weight 89054, molecular weight distribution 1.88.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag
+electrode is reference electrode, Bu
4nPF
6make ionogen, in acetonitrile solvent, through the initial oxidation current potential of cyclic voltammetry polymer A
for 0.56V (referring to Fig. 2), polymer A ' initial oxidation current potential
for 0.54V (referring to Fig. 1), can calculation formula-(4.72+ initial oxidation current potential/V) eV according to HOMO, the HOMO that obtains polymer A can be-5.28eV, than the materials A of fluoro not '-5.26eV, low 0.02eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61the sandwich battery structure of BM/LiF/Al, by polymer A and acceptor material PC
61bM makes photovoltaic cell according to certain weight ratio, useful area 0.0314cm
2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.75V, photoelectric transformation efficiency is 2.78%.
Embodiment 2: polymer B
Synthetic route is as follows:
Fluoro-5 with 6,7-bis-in this embodiment, 8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline is short of electricity unit, adopts the polymerization process in embodiment 1 step 3 to prepare polymer B, and its productive rate is 85%, number-average molecular weight 58563, molecular weight distribution 1.96.Wherein 6,7-bis-is fluoro-5,8-bis-bromo-2, the preparation method of 3-bis-(3-octyloxyphenyl) quinoxaline adopts the method in embodiment 1 step 1, and difference is with 4,5-bis-fluoro-3,6-bis-bromo-1,2-phenylenediamine replaces 4-fluoro-3, and 6-bis-is bromo-1,2-phenylenediamine, make 6,7-bis-is fluoro-5, and 8-bis-is bromo-2, and the nuclear-magnetism characterization data of 3-bis-(3-octyloxyphenyl) quinoxaline is:
1hNMR (CDCl
3, 500MHz, ppm), δ=7.32 (m, 4H), 7.24 (t, 2H), 6.98 (m, 2H), 3.95 (t, 4H) 1.76 (m, 4H), 1.45 (dd, 4H), 1.34 (m, 16H), 0.93 (t, 6H).
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag
+electrode is reference electrode, Bu
4nPF
6make ionogen, in acetonitrile solvent, through the HOMO of cyclic voltammetry polymer B film can be-5.34eV, than the materials A of fluoro not '-5.26eV, low 0.08eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61the sandwich battery structure of BM/LiF/Al, by polymer B and acceptor material PC
61bM makes photovoltaic cell according to certain weight ratio, useful area 0.0314cm
2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.76V, photoelectric transformation efficiency is 3.28%.
Embodiment 3: polymkeric substance C
Synthetic route is as follows:
This embodiment is fluoro-5 with 6-, and 8-bis-is bromo-2, and 3-bis-(4-octyloxyphenyl) quinoxaline is short of electricity unit, adopts the method in embodiment 1 step 3 to prepare polymkeric substance C, productive rate 85%, number-average molecular weight 45315, molecular weight distribution 2.11.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag
+electrode is reference electrode, Bu
4nPF
6make ionogen, in acetonitrile solvent, through the HOMO of cyclic voltammetry polymkeric substance C film can be-5.20eV, than the material B of fluoro not '-5.16eV, low 0.04eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61the sandwich battery structure of BM/LiF/Al, by polymkeric substance C and acceptor material PC
61bM makes photovoltaic cell according to certain weight ratio, useful area 0.0314cm
2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.72V, photoelectric transformation efficiency is 2.97%.
Embodiment 4: polymkeric substance D
Synthetic route is as follows:
This embodiment is fluoro-5 with 6,7-bis-, and 8-bis-is bromo-2, and 3-bis-(4-octyloxyphenyl) quinoxaline is short of electricity unit, adopts identical polymerization process to obtain polymkeric substance D, productive rate 89.2%, number-average molecular weight 65328, molecular weight distribution 1.93.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag
+electrode is reference electrode, Bu
4nPF
6make ionogen, in acetonitrile solvent, through the HOMO of cyclic voltammetry polymkeric substance D film can be-5.24eV, than the material B of fluoro not '-5.16eV, low 0.08eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61the sandwich battery structure of BM/LiF/Al, by polymkeric substance D and acceptor material PC
61bM makes photovoltaic cell according to certain weight ratio, useful area 0.0314cm
2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.78V, photoelectric transformation efficiency is 3.45%.
Embodiment 5: polymkeric substance E
Synthetic route is as follows:
This embodiment is fluoro-5 with 6-, and 8-bis-is bromo-2, and 3-bis-(5-octyl group thiophene) quinoxaline is shortcoming unit, adopts the method polymkeric substance E in embodiment 1 step 3, productive rate 87%, number-average molecular weight 85216, molecular weight distribution 1.85.
Wherein 6-is fluoro-5, and 8-bis-is bromo-2, and the preparation process of 3-bis-(5-octyl group thiophene) quinoxaline is:
1,2-bis-(5-octyl group thiophene) second diketone (3g, 6.7mmol) and 4-fluoro-3,6-bis-is bromo-1, and 2-phenylenediamine (2.28g, 8.04mmol) 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 group thiophene) quinoxaline 3.31g, productive rate 71%, nuclear-magnetism characterization data:
1h NMR (CDCl
3, 500MHz, ppm), δ=7.81 (d, 1H), 7.45 (dd, 2H), 6.78 (d, 2H), 2.93 (t, 4H), 1.78 (m, 4H), 1.46 (dd, 4H), 1.35-1.30 (m, 16H), 0.92 (t, 6H).
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag
+electrode is reference electrode, Bu
4nPF
6make ionogen, in acetonitrile solvent, through the HOMO of cyclic voltammetry polymkeric substance E film can be-5.30eV, than the material C of fluoro not '-5.24eV, low 0.06eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61the sandwich battery structure of BM/LiF/Al, by polymkeric substance E and acceptor material PC
61bM makes photovoltaic cell according to certain weight ratio, useful area 0.0314cm
2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.79V, photoelectric transformation efficiency is 2.89%.
Embodiment 6: polymkeric substance F
Synthetic route is as follows:
This embodiment is fluoro-5 with 6,7-bis-, and 8-bis-is bromo-2, and 3-bis-(5-octyl group thiophene) quinoxaline is short of electricity unit, adopts the method in embodiment 1 step 3 to prepare polymkeric substance F, productive rate 87.5%, number-average molecular weight 66954, molecular weight distribution 2.04.Wherein, 6,7-bis-fluoro-5,8-bis-is bromo-2, and in the preparation method of 3-bis-(5-octyl group thiophene) quinoxaline and embodiment 5,6-is fluoro-5,8-bis-bromo-2, the preparation method of 3-bis-(5-octyl group thiophene) quinoxaline is identical, and difference is with 4,5-bis-fluoro-3,6-bis-is bromo-1, and 2-phenylenediamine replaces 4-fluoro-3,6-bis-bromo-1,2-phenylenediamine, make 6,7-bis-fluoro-5,8-bis-is bromo-2, the nuclear-magnetism characterization data of 3-bis-(5-octyl group thiophene) quinoxaline: 1H NMR (CDCl
3, 500MHz, ppm), δ=7.49 (dd, 2H), 6.81 (d, 2H), 2.95 (t, 4H), 1.78 (m, 4H), 1.47 (dd, 4H), 1.35-1.30 (m, 16H), 0.94 (t, 6H).
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag
+electrode is reference electrode, Bu
4nPF
6make ionogen, in acetonitrile solvent, through the HOMO of cyclic voltammetry polymkeric substance F film can be-5.33eV, than the material C of fluoro not '-5.24eV, low 0.09eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61the sandwich battery structure of BM/LiF/Al, by polymkeric substance F and acceptor material PC
61bM makes photovoltaic cell by certain weight ratio, useful area 0.0314cm
2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.83V, photoelectric transformation efficiency 3.75%.
The HOMO energy level of table 1 polymkeric substance
Claims (4)
1. one kind 4, the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline, is characterized in that, the general structure of this polymkeric substance is as shown in formula I:
In formula I,
R
1for: H atom or F atom;
R
2for: carbonatoms is 2-alkylthrophene base or 2, the 3-dialkyl group thienyl of 4 to 20 straight or branched.
2. as claimed in claim 14, the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline, is characterized in that, the structural formula of this polymkeric substance is as shown in formula II:
3. as claimed in claim 14, the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline, is characterized in that, the structural formula of this polymkeric substance is as shown in formula III:
As described in arbitrary claim in claims 1 to 34, the conjugated polymers of 8-bis-octane-iso oxygen base phenyl [1,2-b:4,5-b '] bithiophenes and fluoro quinoxaline is for the preparation of the application of polymer photovoltaic cell.
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