CN102838733B - Conjugated polymer of 9,9-dioctyl fluorene and fluorinated quinoxaline - Google Patents

Conjugated polymer of 9,9-dioctyl fluorene and fluorinated quinoxaline Download PDF

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CN102838733B
CN102838733B CN201210317002.4A CN201210317002A CN102838733B CN 102838733 B CN102838733 B CN 102838733B CN 201210317002 A CN201210317002 A CN 201210317002A CN 102838733 B CN102838733 B CN 102838733B
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quinoxaline
bis
fluoro
polymer
fluorinated
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CN102838733A (en
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高潮
武海梅
刘红利
陈键
王户生
安忠维
陈冬
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Xian Modern Chemistry Research Institute
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Abstract

The purpose of the invention is to use the electron-withdrawing property of fluorine atoms to develop a new type fluorinated quinoxaline containing D-A-D donating polymer material to reduce the HOMO energy level of the polymer material. The invention discloses a conjugated polymer of 9,9-dioctyl fluorene and fluorinated quinoxaline, the structural formula of which is shown in the specification, wherein in the formula, R1 is an H or F atom; R2 is alkoxyl phenyl of a straight chain or a branched chain with meta or para-position carbon atom number of 4 to 20, or 2-alkylated thiophene or 2,3-dialkyl thiophene of a straight chain or a branched chain with carbon atom number of 4 to 20; and R3 is alkyl group of a straight chain or a branched chain with H or C atom number of 4-20. Compared with the corresponding non-fluorinated polymer, the HOMO energy level of the single fluorine polymer is 0.02-0.2eV lower than that of the non-fluorinated polymer, the HOMO energy level of the double fluorine polymer is 0.05-0.3eV lower than that of the non-fluorinated polymer.

Description

The conjugated polymers of 9,9-dioctyl fluorene and fluoro quinoxaline
Technical field
The invention belongs to filed of functional, be specifically related to the conjugated polymers of a kind of 9,9-dioctyl fluorene and fluoro quinoxaline.
Background technology
Along with the growth of socioeconomic development and population, to the demand rising of the energy, and limited as the energy reserve of representative taking coal, oil, just become more and more urgent so develop reproducible new forms of energy.As a kind of green, the energy-sun power reliably, the common concern that it utilizes, exploitation has been subject to international community.Polymer solar battery has that 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 this area research is the efficient donor material of exploitation and acceptor material, and acceptor material is defined as the derivative of C60 at present substantially as PC61BM and PC71BM, that therefore develops excellent property becomes the emphasis of current research to body polymkeric substance.For this reason, a kind of method that the D-A-D type polymkeric substance that the main chain of conjugated polymers forms is alternately introduced in electron rich unit (D) and electron deficiency unit (A) becomes the Main Means of current exploitation to body polymkeric substance.
Within 2003, Takakazu Yamamoto shifts quinoxaline and 2 in order to realize intramolecular electric charge, the polymerization of 5-bis-(tin trimethyl) thiophene reagent, by the test of the absorption to material and luminous energy, find that first this class material has strong and wide absorption in long wave direction, and foretold its potential application in following photoelectric device.Quinoxaline and derivative thereof, as the novel short of electricity unit of a class, receive much concern in recent years and obtain synthetic TQ1 and the PCBM blend such as good achievement, such as Ergang Wang, photoelectric transformation efficiency reaches 6.0%, [advanced material Adv.Mater.2010,22 (46), 5240-5244].Open circuit voltage is the principal element that affects device performance, and the HOMO energy level of donor material is determining the open circuit voltage of device, and in order to reduce the HOMO energy level to body, the fluorine atom of tool strong electronegativity is often introduced in short of electricity unit, and has obtained remarkable achievement.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].The HOMO energy level of the synthetic PBDTT-C of the people such as Yang yang be-5.12ev, the be reduced to-5.22ev of HOMO energy level of PBDTT-CF after introducing fluorine atom, and open circuit voltage rises to 0.76V by 0.7V, [natural photon Nature Photonics..2009,3,649-653].Based on above-mentioned theory and achievement in research, on this electron deficiency of quinoxaline unit, introducing fluorine atom prepares novel fluorine-containing D-A-D type and is expected to further reduce HOMO to body polymkeric substance, promote open circuit voltage, thereby improve device photovoltaic performance, 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
For the deficiencies in the prior art, the object of the invention is to develop a kind of novel D-A-D type that contains fluoro quinoxaline to body polymer materials, meet the needs of polymer photovoltaic cell photoactive layers electron donor material.
Another object of the present invention is to utilize the electrophilic characteristic of 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:
The conjugated polymers of a kind of 9,9-dioctyl fluorene and fluoro quinoxaline, its general structure is suc as formula shown in I:
(formula I),
In formula, R 1h or F atom; R 2between being, position or para-position carbon atomicity are the alkoxyl phenyl of 4 to 20 straight or branched, or carbonatoms is 2-alkylthrophene or 2, the 3-dialkyl group thienyl of 4 to 20 straight or branched; R 3that H or carbonatoms are the alkyl of 4 to 20 straight or branched.
The present invention also has following technical characterstic:
Described 9, the structure of the conjugated polymers of 9-dioctyl fluorene and fluoro quinoxaline is suc as formula shown in II:
(formula II).
Described 9, the structure of the conjugated polymers of 9-dioctyl fluorene and fluoro quinoxaline is suc as formula shown in III:
(formula III).
Described 9, the structure of the conjugated polymers of 9-dioctyl fluorene and fluoro quinoxaline is suc as formula shown in IV:
(formula IV).
Described 9, the structure of the conjugated polymers of 9-dioctyl fluorene and fluoro quinoxaline is suc as formula shown in V:
(formula V).
Described 9, the structure of the conjugated polymers of 9-dioctyl fluorene and fluoro quinoxaline is suc as formula shown in VI:
(formula VI).
Described 9, the structure of the conjugated polymers of 9-dioctyl fluorene and fluoro quinoxaline is suc as formula shown in VII:
(formula VII).
Described 9, the conjugated polymers of 9-dioctyl fluorene and fluoro quinoxaline is for the preparation of the application of polymer photovoltaic cell.
To achieve these goals, disclosed by the invention 9, the conjugated polymers of 9-dioctyl fluorene and fluoro quinoxaline, carries out according to reaction formula as follows:
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 remove ethanol with distillation under vacuum afterwards, adds suitable quantity of water, ethyl acetate extraction, organic phase anhydrous magnesium sulfate drying, crude product silicagel column purifying 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.
By above-mentioned 6 or 6,7 fluorine-containing 5,8-bis-is bromo-2,3-bis-R 2base quinoxaline and 4-R 3base thiophene-2-tributyl tin is by Stille linked reaction, and products therefrom is taking DMF/THF as solvent, carries out bromo with NBS, obtain 6 or 6,7 fluorine-containing 5,8-bis-(the bromo-2-R of 5- 3base thiophene)-2, the disubstituted quinoxaline of 3-.
The preparation of the conjugated polymers of (2) 9,9-dioctyl fluorene and fluoro quinoxaline
This reaction is carried out under nitrogen protection, to be subject to body unit 6 or 6, 7 fluorine-containing 5, 8-bis-(5-bromothiophene base)-2, the molar weight of the disubstituted quinoxaline of 3-is as matching criterion, with 9 of equimolar amount, 9-dioctyl-2, 7-bis-fluorenes boric acid esters, 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 backflow 72h, inject bromobenzene and add phenylo boric acid end-blocking, reaction 24h.Stopped reaction, system is cooled to room temperature, reaction solution is splashed into sedimentation in methyl alcohol, filter, at 50 DEG C of the polymkeric substance vacuum drying ovens of collection, dry 12h, carry out soxhlet extraction with methyl alcohol, normal hexane, chloroform successively, concentrated chloroform extracted solution, with methyl alcohol sedimentation again, filters, obtain suc as formula 9 shown in I the conjugated polymers of 9-dioctyl fluorene and fluoro quinoxaline.
The present invention adopts fluorine-containing quinoxaline and derivative thereof as short of electricity unit, 9,9-dioctyl fluorene boric acid ester, as giving electric unit, has synthesized 9 of single fluoro and two fluoro by Suzuki coupling, the conjugated polymers (in table 1, A～F) of 9-dioctyl fluorene and fluoro quinoxaline.By cyclic voltammetric characteristic test, with 9 of fluoro not, the conjugated polymers of 9-dioctyl fluorene-quinoxaline is (in table 1, A '～C ') compare, draw following result: the HOMO energy level of single fluoropolymer is the low 0.02～0.2eV of polymkeric substance of fluoro more not, the HOMO energy level of two fluorinated polymers is the low 0.05～0.3eV of polymkeric substance of fluoro more not.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
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 of doing on present techniques scheme basis all fall into protection scope of the present invention.
Embodiment 1: short of electricity unit fluorine-containing quinoxaline series preparation
Fluoro-5 with 6-, 8-bis-is bromo-2, and 3-bis-(3-octyloxyphenyl) quinoxaline and 6-are fluoro-5,8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(3-octyloxyphenyl) quinoxaline be prepared as example, 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 under 00C in batches 4(11.1g, 0.29mol), then reacts 20h under room temperature.After reaction finishes, adopt distillation under vacuum to remove ethanol, add 160ml water, be extracted with ethyl acetate, saturated common salt water washing organic phase, finally uses anhydrous MgSO 4dry.The concentrated organic solvent of removing, obtain thick for product n-hexane/ethyl acetate (normal hexane is 25:1 with the volume ratio of ethyl acetate) silica gel column chromatography separate, obtain 4-fluoro-3,6-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 30.2mmol), (40ml) adds 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 reaction 30min.In system, add saturated NH 4cl solution cancellation reaction, is extracted with ethyl acetate salt water washing organic phase, anhydrous MgSO 4dry, the concentrated organic solvent of removing, obtain thick for product n-hexane/ethyl acetate (normal hexane is 200:1 with the volume ratio of ethyl acetate) silica gel column chromatography separate, obtain 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-octyloxyphenyl) 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 is: 1h NMR (500MHz, CDCl3, 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).
(4) 6-is fluoro-5,8-bis-(5-bromothiophene)-2, the preparation of 3-bis-(3-octyloxyphenyl) quinoxaline
6-is fluoro-5, and 8-bis-is bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline (1.26g, 1.76mmol), 2-tributyl tin thiophene (1.44g, 3.88mmol) and Pd (PPh 3) Cl 2(0.049g, 0.046mmol) is dissolved in 20ml toluene, N 2the lower back flow reaction 24h of protection.Concentrated toluene, crude product normal hexane recrystallization, obtains safran solid 6-fluoro-5,8-bis-thiophene-2,3-bis-(3-octyloxyphenyl) quinoxaline (1.01g, 80%).
6-is fluoro-5,8-bis-(5-bromothiophene)-2, and 3-bis-(3-octyloxyphenyl) quinoxaline (0.5g, 0.7mmol), NBS (0.261g, 1.47mmol) is dissolved in 20mlDMF, 40 ° of C reaction 7h.Cooling, suction filtration, methanol wash filter cake.Crude product normal hexane recrystallization, obtains 6-fluoro-5,8-bis-(5-bromothiophene)-2,3-bis-(3-octyloxyphenyl) quinoxaline 0.43g, productive rate 70%.
Nuclear-magnetism characterization data is: 1h NMR (CDCl 3, 500MHz, ppm): δ=7.90 (d, 1H, J=15Hz), 7.77 (d, 1H, J=3.5Hz), 7.53 (dd, 3H, J=10Hz), 7.22 (ddd, 2H, J=5Hz), 7.14 (dd, 2H, J=5Hz), 7.09 (d, 2H, J=5Hz), 6.98 (d, 2H, J=5Hz), 4.04 (q, 4H), 1.80 (m, 4H), 1.49 (m, 4H), 1.33 (m, 16H), 0.89 (t, 6H, J=5Hz).
As mentioned above, utilize identical method to prepare 6-fluoro-5,8-bis-(5-bromothiophene)-2,3-bis-(4-octyloxyphenyl) quinoxaline and 6-fluoro-5,8-bis-(5-bromothiophene)-2,3-bis-(5-octyl group thiophene) quinoxaline.
Embodiment 2:9,9-dioctyl-2, the preparation of 7-bis-fluorenes boric acid esters
With 2; 7-dibromo fluorenes is raw material; according to synthetic 9, the 9-of traditional method dioctyl-2, after 7-dibromo fluorenes; this compound (5g; 9.1mmol) under nitrogen protection, join in 70mlTHF, system is cooled under-78 ° of C, drip 2.2M butyllithium 8.7mL; dropwise; be warming up to 0 DEG C, at this temperature, react after 15min, system is cooled to-78 DEG C again; the disposable Virahol pinacol boric acid ester (4.2g that adds; 21.7mmol), reaction solution reacts after 24h under room temperature, pours in frozen water; extracted with diethyl ether, organic phase is with salt water washing and use anhydrous MgSO 4dry, concentrated solvent, crude product THF:CH 3oH=1:1(volume ratio) recrystallization, obtain 9,9-dioctyl-2,7-bis-fluorenes boric acid ester 3.1g, productive rate 53%.
Nuclear-magnetism characterization data is: 1h NMR (CDCl 3, 500MHz, ppm), δ=7.84 (d, 2H), 7.78 (s, 2H), 7.75 (d, 2H), 2.03 (m, 4H), 1.43 (s, 24H), 1.26-1.04 (m, 20H), 0.83 (t, 6H), 0.58 (m, 4H).
Embodiment 3: polymer A
Whole reaction is carried out under nitrogen protection, 6-fluoro-5, 8-bis-(5-bromothiophene)-2, 3-bis-(3-octyloxyphenyl) quinoxaline (263mg, 0.3mmol) He 9, 9-dioctyl-2, 7-bis-fluorenes boric acid ester (192.7mg, 0.3mmol) be dissolved in 10ml toluene, inject the tetraethylamine hydroxide solution that 2.3ml massfraction is 20%, logical nitrogen 0.5h, add catalyzer three (diphenylmethylene acetone) two palladiums (5.5mg) and part tri-o-tolyl phosphorus (9.8mg), continue to start heating after ventilation 0.5h, back flow reaction 72h, inject 3.3 μ l bromobenzene end-blockings, after 1h, add phenylo boric acid 3.6mg, reaction 24h.By at room temperature naturally cooling of the polymkeric substance obtaining, dropwise add to sedimentation in methyl alcohol, filter, at 50 DEG C of the polymkeric substance vacuum drying ovens of collection, dry 12h, the polymkeric substance obtaining is used methyl alcohol, normal hexane, chloroform soxhlet extraction successively, concentrated chloroform extracted solution, drops to sedimentation in methyl alcohol again, obtains (polymer A) 253mg, for the fibrous solid of burgundy, productive rate 75%, number-average molecular weight 37132, distribution coefficient 2.76.
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 film for 0.65V, polymer A ' initial oxidation current potential for 0.58V, according to the calculation formula of HOMO energy level-(4.72+ initial oxidation current potential/V) eV, the HOMO energy level that obtains polymer A is-5.37eV, than the respective material A ' of fluoro not-5.30eV, low 0.07eV, in table 1 and accompanying drawing.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich type 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 Oriel 69911 simulated solar light sources, carry out performance test, utilize Keithley 2611 source tables to gather, open circuit voltage is 0.82V, photoelectric transformation efficiency is 3.25%.
Embodiment 4: polymer B
With embodiment 3, just by short of electricity unit 6-fluoro-5,8-bis-(5-bromothiophene)-2,3-bis-(3-octyloxyphenyl) quinoxaline changes 6,7-bis-fluoro-5 into, 8-bis-(5-bromothiophene)-2,3-bis-(3-octyloxyphenyl) quinoxaline, adopts identical polymerization process to obtain polymer B, productive rate 75.5%, number-average molecular weight 34562, distribution coefficient 2.12.
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-5.40eV, than the respective material A ' of fluoro not-5.30eV, low 0.10eV, 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 part by weight, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out current-voltage test, utilize Keithley 2611 source tables to gather, open circuit voltage is 0.85V, photoelectric transformation efficiency is 3.31%.
Embodiment 5: polymkeric substance C
With embodiment 3, just by short of electricity unit 6-fluoro-5,8-bis-(5-bromothiophene)-2, it is fluoro-5 that 3-bis-(3-octyloxyphenyl) quinoxaline changes 6-into, 8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(4-octyloxyphenyl) quinoxaline, adopt and obtain polymkeric substance C with the identical polymerization process of embodiment 3, productive rate 78%, number-average molecular weight 23145, distribution coefficient 2.33.
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-5.30eV, than the respective material B ' of fluoro not-5.23eV, low 0.07eV, 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 part by weight, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out current-voltage test, utilize Keithley 2611 source tables to gather, open circuit voltage is 0.76V, photoelectric transformation efficiency is 2.78%.
Embodiment 6: polymkeric substance D
With embodiment 5, just by fluoro-6-5,8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(4-octyloxy benzene) quinoxaline changes 6,7-bis-fluoro-5 into, 8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(4-octyloxyphenyl) quinoxaline, adopts identical polymerization process to obtain polymkeric substance D, productive rate 80.2%, number-average molecular weight 32145, distribution coefficient 2.46.
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-5.36eV, than the respective material B ' of fluoro not-5.23eV, low 0.13eV, 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 part by weight, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out current-voltage test, utilize Keithley 2611 source tables to gather, open circuit voltage is 0.82V, photoelectric transformation efficiency is 3.11%.
Embodiment 7: polymkeric substance E
With embodiment 3, just by short of electricity unit 6-fluoro-5,8-bis-(5-bromothiophene)-2, it is fluoro-5 that 3-bis-(3-octyloxyphenyl) quinoxaline changes 6-into, 8-bis-(5-bromothiophene)-2,3-bis-(5-octyl group thiophene) quinoxaline, adopt identical polymerization process to obtain polymkeric substance E, productive rate 78%, number-average molecular weight 36541, distribution coefficient 3.11.
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 E film can be-5.36eV, than the respective material C ' of fluoro not-5.32eV, 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 E and acceptor material PC 61bM makes photovoltaic cell according to certain part by weight, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out current-voltage test, utilize Keithley 2611 source tables to gather, open circuit voltage is 0.81V, photoelectric transformation efficiency is 3.02%.
Embodiment 8: polymkeric substance F
With embodiment 7, by fluoro-6-5,8-bis-(5-bromothiophene)-2,3-bis-(5-octyl group thiophene) quinoxaline changes 6,7-bis-fluoro-5 into, 8-bis-(5-bromothiophene)-2,3-bis-(5-octyl group thiophene) quinoxaline, adopts identical polymerization process to obtain polymkeric substance F, productive rate 81.2%, number-average molecular weight 34127, distribution coefficient 2.41.
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-5.41eV, than the respective material C ' of fluoro not-5.32eV, 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 according to certain part by weight, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out current-voltage test, utilize Keithley 2611 source tables to gather, open circuit voltage is 0.86V, photoelectric transformation efficiency is 3.78%.
The HOMO energy level of table 1 polymkeric substance

Claims (4)

1. a conjugated polymers, is characterized in that, general structure is suc as formula shown in I:
(formula I),
In formula, R 1h or F atom; R 2between being, position or para-position carbon atomicity are the alkoxyl phenyl of 4 to 20 straight or branched, or carbonatoms is 2-alkylthrophene base or 2, the 3-dialkyl group thienyl of 4 to 20 straight or branched; R 3that carbonatoms is the alkyl of 4 to 20 straight or branched.
2. conjugated polymers as claimed in claim 1, is characterized in that, the structure of described conjugated polymers is suc as formula shown in IV:
(formula IV).
3. conjugated polymers as claimed in claim 1, is characterized in that, the structure of described conjugated polymers is suc as formula shown in V:
(formula V).
4. the conjugated polymers as described in arbitrary claim in claims 1 to 3 is for the preparation of the application of polymer photovoltaic cell.
CN201210317002.4A 2012-08-30 2012-08-30 Conjugated polymer of 9,9-dioctyl fluorene and fluorinated quinoxaline Expired - Fee Related CN102838733B (en)

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