CN102827356B - The conjugated polymers of 9-heptadecyl carbazole and fluoroquinoxaline - Google Patents

The conjugated polymers of 9-heptadecyl carbazole and fluoroquinoxaline Download PDF

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CN102827356B
CN102827356B CN201210316918.8A CN201210316918A CN102827356B CN 102827356 B CN102827356 B CN 102827356B CN 201210316918 A CN201210316918 A CN 201210316918A CN 102827356 B CN102827356 B CN 102827356B
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heptadecyl
fluoroquinoxaline
carbazole
bis
conjugated polymers
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CN102827356A (en
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高潮
刘红利
武海梅
刘建群
王户生
安忠维
陈键
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Xian Modern Chemistry Research Institute
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Abstract

The invention belongs to organic polymer field of functional materials, be specially the conjugated polymers of a kind of 9-heptadecyl carbazole and fluoroquinoxaline derivative, its general structure is shown below:

Description

The conjugated polymers of 9-heptadecyl carbazole and fluoroquinoxaline
Technical field
The invention belongs to functional high polymer material field, be specifically related to the conjugated polymers of a kind of 9-heptadecyl carbazole and fluoroquinoxaline.
Background technology
The intensification day by day of the environmental pollution caused along with energy dilemma and combustion of fossil fuels, receives more concern to the exploitation of renewable energy source.Polymer solar battery because its preparation process is simple, cost is low, lightweight and can the outstanding advantages such as flexible device be prepared into, become domestic and international study hotspot in recent years, the focus of present polymer solar cell research be the efficient conjugated polymers of exploitation to body and acceptor material to improve its photovoltaic energy conversion efficiency.For the polymer materials serving as electron donor(ED), the absorption spectrum of material determines the short-circuit current of device, and the HOMO energy level of material determines the open circuit voltage of device, and the structure of material and carrier mobility determine the packing factor of device.In order to obtain donor polymer material of good performance, 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.
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, such as Cao Yong etc. synthesize PECz-DTQX, blended with PCBM, electricity conversion is for reaching 6.07%, [advanced material Adv.Mater.2011,23 (27), 3086-3089].
In order to improve the photoelectric transformation efficiency of polymer solar battery further, under the prerequisite ensureing large short-circuit current, the open circuit voltage of enhance device is inevitable selection.Research in recent years shows, will have the highest occupied molecular orbital energy (HOMO energy) that effectively can reduce material by body unit of the fluorine atom introducing donor polymer haling electrical property, and then can promote the open circuit voltage of battery.As 2009, the people such as Hou Jianhui by PBDTTT-C by body unit introducing draw electric group F atom to obtain polymer P BDTTT-CF, the HOMO of material can be reduced to-5.22eV by-5.12eV, open circuit voltage has brought up to 0.76V [Nat.Photon.2009 by 0.7V, 3,649-653].2010, the people such as Luping Yu at its donor material PTBF0 researched and developed by body unit introduces fluorine atom, obtain polymer P TBF1, the HOMO of material can be reduced to-5.15eV by-4.94eV, open circuit voltage has brought up to 0.74V [J.Am.Chem.Soc.2011 by 0.58V, 133,1885-1894].
Fluorine atom is on the impact of material property in view of the above, this electron deficiency of quinoxaline unit is introduced fluorine atom prepare novel fluorine-containing D-A-D type donor polymer be expected to reduce further HOMO can, promote open circuit voltage, thus improve device photovoltaic performance, but yet there are no so far about the structure of this type of material, preparation method 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, the conjugated polymers of a kind of 9-heptadecyl carbazole and fluoroquinoxaline is provided, this conjugated polymers is by 9-heptadecyl-2,7-carbazole is as giving electric unit, two bromine replaces fluoroquinoxaline monomer as short of electricity unit, is obtained, can be used in the donor material of bulk heteroj joint solar cell by Suzuki linked reaction.This polymkeric substance, owing to introducing strong electron-withdrawing group fluorine atom on electron deficiency unit quinoxaline, effectively can reduce material HOMO energy level, thus promotes the open circuit voltage of polymer photovoltaic cell.
To achieve these goals, the present invention adopts following technical solution:
A conjugated polymers for 9-heptadecyl carbazole and fluoroquinoxaline, the general structure of described conjugated polymers is such as formula shown in I:
In formula, R 1: H or F atom;
R 2: a 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;
R 3: H or carbonatoms are the straight or branched alkyl of 1 to 20.
Preferred polymer A in described 9-heptadecyl carbazole and the conjugated polymers of fluoroquinoxaline, its structure is such as formula shown in II:
Preferred polymer B in described 9-heptadecyl carbazole and the conjugated polymers of fluoroquinoxaline, its structure is such as formula shown in III:
Preferred polymkeric substance C in described 9-heptadecyl carbazole and the conjugated polymers of fluoroquinoxaline, its structure is such as formula shown in IV:
Preferred polymkeric substance D in described 9-heptadecyl carbazole and the conjugated polymers of fluoroquinoxaline, its structure is such as formula shown in V:
Preferred polymkeric substance E in described 9-heptadecyl carbazole and the conjugated polymers of fluoroquinoxaline, its structure is such as formula shown in VI:
Described 9-heptadecyl carbazole and the preferred polymkeric substance F of the conjugated polymers of fluoroquinoxaline, its structure is such as formula shown in VII:
Preferred polymkeric substance G in described 9-heptadecyl carbazole and the conjugated polymers of fluoroquinoxaline, its structure is such as formula shown in VIII:
Preferred polymkeric substance H in described 9-heptadecyl carbazole and the conjugated polymers of fluoroquinoxaline, its structure is such as formula shown in Ⅸ:
Described 9-heptadecyl carbazole and the conjugated polymers of fluoroquinoxaline derivative, its polyreaction adopts the reaction equation as shown in Scheme 1 to carry out.
Concrete synthesis step is as follows:
(1) by the preparation of the fluorine-containing quinoxaline of body 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 react 20h under room temperature, reaction terminates rear concentrated removing ethanol, adds suitable quantity of water, extraction into ethyl acetate, organic phase anhydrous magnesium sulfate drying, crude product selects purification by silica gel column chromatography, obtains fluorinated diamine, then with 1,2-bis-R 2base second diketone take acetic acid as solvent reaction, obtained 6 or 6,7 fluorine-containing 5,8-bis-bromo-2,3-bis-R 2base quinoxaline.
By above-mentioned 6 or 6,7 fluorine-containing 5,8-bis-bromo-2,3-bis-R 2base quinoxaline and 4-R 3base-2-tributyl tin thiophene is by Stille linked reaction, and products therefrom take DMF/THF as solvent, carries out bromo with NBS, obtains 6 or 6,7 fluorine-containing 5,8-bis-(bromo-4-R of 5- 3base thiophene)-2,3-disubstituted quinoxalines.
(2) preparation of donor monomer 9-heptadecyl-2,7-carbazole boric acid ester
2,7-dibromo carbazole is dissolved in DMSO, in the basic conditions, is obtained by reacting 9-heptadecyl-2,7-dibromo carbazole.9-heptadecyl-2,7-dibromo carbazole is dissolved in THF, cools to less than-78 DEG C, add n-Butyl Lithium, react 1h at-78 DEG C after, directly add 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-bis-Evil, after having reacted, obtains 9-heptadecyl-2,7-carbazole boric acid ester.
(3) preparation of polymkeric substance
This reaction is carried out under nitrogen protection, gets a certain amount of by fluorine-containing 5,8-bis-(the bromo-4-R of 5-of body unit 6 replacement 3base thiophene) two fluoro-5,8-bis-(the bromo-4-R of 5-of-2,3-disubstituted quinoxalines or 6,7- 3base thiophene)-2, the disubstituted quinoxaline of 3-, with the 9-heptadecyl-2 of equimolar amount, 7-carbazole boric acid ester and tetraethyl ammonium hydroxide 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 60h, add bromobenzene, phenylo boric acid is added after 1h, back flow reaction 12h again, stopped reaction, system is cooled to room temperature, reaction solution is instilled sedimentation in methyl alcohol, filter, the polymkeric substance vacuum drying oven collected 50 ° of C dry 12h, use methyl alcohol successively, normal hexane, chloroform carries out soxhlet extraction, concentrated chloroform extracted solution, with methyl alcohol sedimentation again, filter, obtain as shown in I containing fluoroquinoxaline and 9-heptadecyl-2, the conjugated polymers of 7-carbazole.The beneficial effect of the conjugated polymers of 9-heptadecyl carbazole of the present invention and fluoroquinoxaline is as follows:
Employing 9-heptadecyl-2,7-carbazole is as giving electric unit, and two bromo fluoroquinoxaline derivative, as short of electricity unit, prepares the conjugated polymers of 9-heptadecyl substituted carbazole and fluoroquinoxaline derivative by Suzuki linked reaction.Utilize cyclic voltammetry, compare with non-fluoroquinoxaline-9-heptadecyl substituted carbazole polymkeric substance (structural formula A ' ~ D ') (see table 1), the low 0.02-0.2eV of the more non-fluoro of HOMO energy level of single fluorinated polymer, the HOMO of two fluorinated polymer can the low 0.05 ~ 0.3eV of more non-fluoro.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.
Another object of the present invention is, by introducing strong electron-withdrawing group group on electron deficiency unit quinoxaline, the HOMO reducing polymer materials can, thus improving the open circuit voltage of photovoltaic cell, the 9-heptadecyl carbazole described in proposition and the conjugated polymers of fluoroquinoxaline are preparing the application in polymer photovoltaic cell.
Accompanying drawing explanation
Fig. 1 is polymer A ' C-V figure;
Fig. 2 is the C-V figure of polymer A;
Below in conjunction with the drawings and specific embodiments, explanation is further explained to the present invention.
Embodiment
In order to understand the present invention better, be described in detail this Macroscopic single crystal and performance respectively below, the cited case does not limit the scope of the invention.
Embodiment 1: by the synthesis of body unit 6-fluoro-5,8-bis-(5-bromothiophene)-2,3-bis-(3-octyloxyphenyl) quinoxaline
Synthetic route is as follows:
(1) synthesis of fluoro-3,6-bis-bromo-1, the 2-phenylenediamines (compound 1) of 4-
Fluoro-4,7-bis-bromo-2,1, the 3-diazosulfides (5g, 16mmol) of 5-are dissolved in dehydrated alcohol (150ml), add NaBH at 0 DEG C in batches 4(11.1g, 290mol), then at room temperature reacts 20h.After reaction terminates, concentrated removing ethanol, adds 160ml water, extraction into ethyl acetate, saturated common salt water washing organic phase, anhydrous MgSO 4drying, concentrate and obtain crude product, with n-hexane/ethyl acetate (25:1, v/v) silica gel column chromatography, obtain 3.5g product (compound 1), yield is 78%.
The synthesis of (2) 1,2-bis-(3-octyloxyphenyl) second diketone (compound 2)
THF(40ml to cuprous bromide (4.33g, 30.2mmol)) add LiBr(5.25g, 60.4mmol in solution), stirred at ambient temperature dissolves, and ice bath is cooled to 0 DEG C, a Grignard reagent [bromobenzene octyl ether (8.6g of bromobenzene octyl ether between dropping, 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, obtain crude product, with n-hexane/ethyl acetate (200:1, v/v) silica gel column chromatography, obtain 1,2-bis-(3-octyloxyphenyl) second diketone 3.46g(compound 2), yield is 55%.
(3) synthesis of fluoro-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline (compounds 3) of 6-
Compound 1(0.59g, 1.9mmol) and compound 2(0.88g, 1.9mmol) be dissolved in 40ml HAc, be warming up to 60 DEG C, close heating, under room temperature, react 2h.Suction filtration, washing with alcohol filter cake, obtains 6-fluoro-5,8-bis-bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline 1.31g(compound 3), yield is 97%.
(4) synthesis of fluoro-5,8-bis-thiophene-2,3-bis-(3-octyloxyphenyl) quinoxalines (compound 4) of 6-
By compound 3(0.821g, 1.15mmol), 2-tributyl tin thiophene (0.918g, 2.46mmol) and Pd (PPh 3) Cl 2(32mg, 0.046mmol) is dissolved in 20ml toluene, N 2protection is lower to reflux reacted night.Concentrated toluene, crude product normal hexane recrystallization, obtains fluoro-5,8-bis-thiophene-2,3-bis-(3-octyloxyphenyl) the quinoxaline 0.66g(compounds 4 of safran solid 6-), yield is 80%.
(5) synthesis of 6-fluoro-5,8-bis-(5-bromothiophene)-2,3-bis-(3-octyloxyphenyl) quinoxaline (compound 5)
By compound 4(0.5g, 0.7mmol) and NBS(0.261g, 1.47mmol) be dissolved in DMF(20ml) in, after being heated to 40 DEG C, insulation reaction 7h, cooling, filter, methanol wash filter cake, obtains fluoro-5,8-bis-(the 5-bromothiophenes)-2 of 6-, 3-bis-(3-octyloxyphenyl) quinoxaline crude product, normal hexane recrystallization, obtain sterling 0.43g (compound 5), yield is 70%.
Nuclear-magnetism characterization data: 1h NMR (500MHz, CDCl 3, ppm): δ=7.89 (d, 1H), 7.77 (d, 1H), 7.53 (dd, 3H), 7.22 (ddd, 2H), 7.14 (dd, 2H), 7.09 (d, 2H), 6.98 (d, 2H), 4.04 (q, 4H), 1.80 (m, 4H), 1.49 (m, 4H), 1.33 (m, 16), 0.89 (t, 6H).
Embodiment 2: the synthesis of donor monomer 9-heptadecyl-2,7-carbazole boric acid ester
Synthetic route is as follows:
(1) synthesis of 9-heptadecyl-2,7-dibromo carbazole (compound 6)
By 2,7-dibromo carbazole (20.3g, 62.5mmol), potassium hydroxide (20.3g, 362.5mmol) and DMSO (160mL) add in the reaction flask of 500mL, pass into N 2, after heating to 40 DEG C, drip the DMSO solution of the 200ml of 9-heptadecyl-p-toluenesulfonic esters (38.6g, 94.1mmol), time 2h, at 40 DEG C of reaction 6h after dripping off.Then poured into by reaction solution in 700mL water, normal hexane extraction, merge organic phase, with saturated common salt rinsing agent to neutral, anhydrous magnesium sulfate drying spends the night.Filter, concentrated, obtain crude product, industrial alcohol recrystallization, obtain white solid 18.2g(compound 6), yield is 51.8%.
(2) synthesis of 9-heptadecyl-2,7-carbazole boric acid ester (compound 7)
Add in 250mL reaction flask by compound 9 (8.2g, 14.6mmol) with THF(150ml), liquid nitrogen cooling is to less than-78 DEG C, add n-Butyl Lithium (19.7ml, 2.2mol/L) with syringe, after adding, at-78 DEG C, react 1h, then 2-isopropoxy-4,4,5 is added, 5-tetramethyl--1,3,2-bis-Evil (8.5g, 43.9mmol), at-78 DEG C, react 1h after adding, be warmed up to room temperature reaction 12h subsequently.Add 100ml water, separate organic phase, aqueous phase anhydrous diethyl ether extracts, and merges organic phase, with saturated common salt rinsing agent to neutral, and anhydrous magnesium sulfate drying.Filter, concentrated, obtain crude product 12.5g.Silica gel column chromatography, n-hexane/ethyl acetate (200:1, v/v) selected by eluent, obtains sterling 4.7g(compound 7), yield is 49%.
Nuclear-magnetism characterization data: 1hNMR (500MHz, CDCl3, ppm): δ=8.122 (m, 2H), 8.02 (s, 1H), 7.88 (s, 1H), 7.66,7.65 (d, 2H), 4.67 ~ 4.71 (m, 1H), 2.31 ~ 2.33 (m, 2H), 1.92 ~ 1.96 (m, 2H), 1.39 (s, 24H), 1.19 ~ 1.22 (m, 10H), 1.12 (m, 12H), 0.96,0.98 (m, 2H), 0.80 ~ 0.83 (t, 6H).
Embodiment 3: polymer A
This reaction is carried out under nitrogen protection, the acceptor unit compound 5(175.8mg that embodiment 1 is obtained, 0.2mmol), the donor monomer compound 7(131.5mg that embodiment 2 obtains, 0.2mmol), tetraethyl ammonium hydroxide (20%, 1.5ml) join with toluene (15ml) in two mouthfuls of dry flasks, ventilation 0.5h, add catalyzer three (dibenzylideneacetone) two palladium (3.7mg) and part tri-o-tolyl phosphorus (6.5mg), continue ventilation 0.5h, then heating is started, after back flow reaction 60h, add 2.2ul bromobenzene, 2.4mg phenylo boric acid is added after 1h, react 12h again, stopped reaction, system is cooled to room temperature, reaction solution is used methyl alcohol sedimentation, filter, obtain polymkeric substance, the dry 12h of vacuum drying oven at 50 DEG C, use methyl alcohol successively, normal hexane, chloroform carries out soxhlet extraction, concentrated chloroform extracted solution, with methyl alcohol sedimentation again, filter, obtain conjugated polymers A(in table 1), yield is 59.3%, number-average molecular weight 22134, distribution coefficient 1.86.
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 0.59V, and polymer A ' initial oxidation current potential for 0.50V, according to HOMO energy calculation formula-(4.72+ initial oxidation current potential/V) eV, the HOMO obtaining polymer A can be-5.31eV, and than-the 5.22eV of the respective material A ' of non-fluoro, low 0.09eV, in table 1 and Fig. 1, Fig. 2.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, by polymer A according to weight ratio 1:5 and acceptor material PC 61bM makes photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light source, carry out current-voltage test, utilize Keithley 2611 source to show to gather, open circuit voltage is 0.82V, short-circuit current density 9.0mA/cm 2, packing factor 0.45, photoelectric transformation efficiency is 3.31%.
Embodiment 4: polymer B
By the synthetic method of body unit with embodiment 1, difference is only fluoro-for 5-wherein 4,7-bis-bromo-2,1,3-diazosulfide changes 5,6-bis-fluoro-4,7-bis-bromo-2 into, 1,3-diazosulfide, synthesizes 6,7-bis-fluoro-5,8-bis-(5-bromothiophene)-2,3-bis-(3-octyloxyphenyl) quinoxaline (compound 8); Donor monomer adopts 9-heptadecyl-2,7-carbazole boric acid ester (compound 7), then, adopts the method described in embodiment 3 to obtain the polymkeric substance that structural formula is B, productive rate 61.4%, number-average molecular weight 24120, distribution coefficient 2.14.
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, can be-5.36eV through the HOMO of cyclic voltammetry polymer B film, than-the 5.22eV 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 polymer B according to certain weight ratio and acceptor material PC 61bM makes photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light source, carry out current-voltage test, utilize Keithley 2611 source to show to gather, open circuit voltage is 0.85V, and photoelectric transformation efficiency is 3.58%.
Embodiment 5: polymkeric substance C
By the synthetic method of body unit with embodiment 1, difference is to change 2-tributyl tin thiophene wherein into 4-hexyl-2-tributyl tin thiophene, according to the synthetic method of synthetic compound 5, synthesize 6-fluoro-5,8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(3-octyloxyphenyl) quinoxaline (compound 9); Donor monomer adopts 9-heptadecyl-2,7-carbazole boric acid ester (compound 7), then, adopts the method described in embodiment 3 to obtain the polymkeric substance that structural formula is C, productive rate 71.6%, number-average molecular weight 15687, distribution coefficient 1.86.
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, can be-5.23eV through the HOMO of cyclic voltammetry polymkeric substance C film, than-the 5.15eV of the respective material B ' of non-fluoro, low 0.08eV, 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 Oriel 69911 simulated solar light source, carry out current-voltage test, utilize Keithley 2611 source to show to gather, open circuit voltage is 0.74V, and photoelectric transformation efficiency is 2.85%.
Embodiment 6: polymkeric substance D
With embodiment 5, difference is fluoro-for 6-5,8-bis-(5-bromo-4-hexyl thiophene)-2,3-bis-(3-octyloxyphenyl) quinoxaline (compound 9) changes 6,7-bis-fluoro-5 into, 8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(3-octyloxyphenyl) quinoxaline (compound 10), adopts the method described in embodiment 5 to obtain the polymkeric substance that structural formula is D, productive rate 69.7%, number-average molecular weight 25312, distribution coefficient 1.91.
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, can be-5.29eV through the HOMO of cyclic voltammetry polymkeric substance D film, than-the 5.15eV of the respective material B ' 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 Oriel 69911 simulated solar light source, carry out current-voltage test, utilize Keithley 2611 source to show to gather, open circuit voltage is 0.81V, and photoelectric transformation efficiency is 3.23%.
Implement 7: polymkeric substance E
With embodiment 1, difference is 1 wherein, 2-bis-(3-octyloxyphenyl) second diketone (compound 2) changes 1 into, 2-bis-(5-octyl thiophene) second diketone, according to the synthetic method of compound 5, synthesize 6-fluoro-5,8-bis-(5-bromothiophene)-2,3-bis-(5-octyl thiophene base) quinoxaline (compound 11); Donor monomer adopts 9-heptadecyl-2,7-carbazole boric acid ester (compound 7), then, adopts the method described in embodiment 3 to obtain the polymkeric substance that structural formula is E, productive rate 70.6%, number-average molecular weight 28453, distribution coefficient 2.17.
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, can be-5.26eV through the HOMO of cyclic voltammetry polymkeric substance E film, than-the 5.20eV of the respective material C ' of non-fluoro, low 0.06eV, 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 Oriel 69911 simulated solar light source, carry out current-voltage test, utilize Keithley 2611 source to show to gather, open circuit voltage is 0.82V, and photoelectric transformation efficiency is 3.45%.
Embodiment 8: polymkeric substance F
With embodiment 7, difference is fluoro-for 6-5,8-bis-(5-bromothiophene)-2,3-bis-(5-octyl thiophene base) quinoxaline (compound 11) changes 6 into, 7-bis-fluoro-5,8-bis-(5-bromothiophene)-2,3-bis-(5-octyl thiophene base) quinoxaline (compound 12), the method described in embodiment 7 is adopted to obtain the polymkeric substance that structural formula is F, productive rate 73.8%.
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, can be-5.35eV through the HOMO of cyclic voltammetry polymkeric substance F film, than-the 5.20eV 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 Oriel 69911 simulated solar light source, carry out current-voltage test, utilize Keithley 2611 source to show to gather, open circuit voltage is 0.86V, and photoelectric transformation efficiency is 3.95%.
Embodiment 9: polymkeric substance G
With embodiment 1, difference is 1 wherein, 2-bis-(3-octyloxyphenyl) second diketone (compound 2) changes 1 into, 2-bis-(5-octyl thiophene) second diketone, 2-tributyl tin thiophene changes 4-hexyl-2-tributyl tin thiophene into, completely according to the synthetic method of synthetic compound 5, synthesizes 6-fluoro-5,8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(5-octyl thiophene) quinoxaline (compound 13); Donor monomer adopts 9-heptadecyl-2,7-carbazole boric acid ester (compound 7), then, adopts the method described in embodiment 3 to obtain the polymkeric substance that structural formula is G, productive rate 67.3%, number-average molecular weight 33127, distribution coefficient 2.08.
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 the solvent of acetonitrile/orthodichlorobenzene=1:5, can be-5.26eV through the HOMO of cyclic voltammetry polymkeric substance G film, than-the 5.17eV of the respective material D ' of non-fluoro, low 0.09eV, 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 G according to certain weight ratio and acceptor material PC 61bM makes photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light source, carry out current-voltage test, utilize Keithley 2611 source to show to gather, open circuit voltage is 0.77V, and photoelectric transformation efficiency is 3.14%.
Embodiment 10: polymkeric substance H
With embodiment 9, difference is fluoro-for 6-5,8-bis-(5-bromo-4-hexyl thiophene)-2,3-bis-(5-octyl thiophene base) quinoxaline (compound 13) changes 6,7-bis-fluoro-5 into, 8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(5-octyl thiophene base) quinoxaline (compound 14), adopts the method described in embodiment 9 to obtain the polymkeric substance that structural formula is H, productive rate 77.1%, number-average molecular weight 21407, distribution coefficient 2.10.
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 the solvent of acetonitrile/orthodichlorobenzene=1:5, can be-5.32eV through the HOMO of cyclic voltammetry polymkeric substance H film, than-the 5.17eV of the respective material D ' 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 H according to certain weight ratio and acceptor material PC 61bM makes photovoltaic cell, useful area 0.0314cm 2, under Newport Thermal Oriel 69911 simulated solar light source, carry out current-voltage test, utilize Keithley 2611 source to show to gather, open circuit voltage is 0.82V, and photoelectric transformation efficiency is 4.31%.
The HOMO energy level of table 1 polymkeric substance

Claims (4)

1. a conjugated polymers for 9-heptadecyl carbazole and fluoroquinoxaline, is characterized in that, the general structure of this conjugated polymers is such as formula shown in I:
In formula, R 1: F atom;
R 2: carbonatoms is 2-alkylthrophene base or 2, the 3-dialkylthiophene base of the straight or branched of 4 to 20;
R 3: H or carbonatoms are the straight or branched alkyl of 1 to 20.
2. the conjugated polymers of 9-heptadecyl carbazole as claimed in claim 1 and fluoroquinoxaline, it is characterized in that, the structure of this conjugated polymers is such as formula shown in III:
3. the conjugated polymers of 9-heptadecyl carbazole as claimed in claim 1 and fluoroquinoxaline, it is characterized in that, the structure of this conjugated polymers is such as formula shown in IV:
4. in claim 1-3, the conjugated polymers of arbitrary described 9-heptadecyl carbazole and fluoroquinoxaline is preparing the application in polymer photovoltaic cell.
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