CN101824042A - Triphenylamine-dithienoindene derivative with photovoltaic property - Google Patents

Triphenylamine-dithienoindene derivative with photovoltaic property Download PDF

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CN101824042A
CN101824042A CN201010125700.5A CN201010125700A CN101824042A CN 101824042 A CN101824042 A CN 101824042A CN 201010125700 A CN201010125700 A CN 201010125700A CN 101824042 A CN101824042 A CN 101824042A
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triphenylamine
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CN101824042B (en
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王筱梅
范丛斌
刘刚
王晓宏
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Suzhou University of Science and Technology
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    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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Abstract

The invention belongs to the field of organic photovoltaic materials and relates to a triphenylamine-dithienoindene derivative, the general formula of the triphenylamine-dithienoindene derivative is shown in the right formula, wherein D represents an electron donor group, in particular to one of the following groups: the vinyl group containing 1 or 3 triphenylamine groups and the styryl group containing 1 or 3 triphenylamine groups. The compound has obvious organic photovoltaic property and a broad-band strong absorption spectral band, absorption spectra of molecules in solution and a solid film show obvious absorption at the band of 200-850nm, the peak positions are distributed at -200nm, -400nm and -700nm, and the absorption spectra are better overlapped with a solar full spectrum, thereby being capable of effectively utilizing the solar full spectrum.

Description

Triphenylamine-two thieno-indene derivative with photovoltaic property
Technical field
The invention belongs to organic photovoltaic material field, relate to a kind of two thieno-indene derivatives that contain trianilino group, this compound has obvious organic photovoltaic characteristic, has strong absorbing band of wide band and tangible organic photovoltaic characteristic.
Background technology
Light/electric the transition material of world energy sources crisis active demand development low cost and less energy-consumption, utilizing the sunlight direct generation of electricity (solar cell) is the important channel that taps a new source of energy.In recent years, country strengthens the investment to the solar energy converting material energetically, in " National Program for Medium-to Long-term Scientific and Technological Development (2006～the year two thousand twenty) ", classify solar energy converting material and technology as country and give priority to one of direction from now on, prove absolutely that development solar energy converting material and technology meet the active demand of national great sector application and Economic development.Traditional solar cell material mainly contains Si series, GaAs series, CdTe series and other inorganic semiconductor material, these materials are with respect to organic semiconductor material, production cost height, material purification contaminate environment are serious, the element manufacturing difficulty of processing is big, and this is a bottleneck of containment inorganic material solar energy battery popularization and application.
Compare with inorganic solar cell, that organic solar batteries has is ultra-thin, in light weight, the organic semiconductor material molecule and level structure is adjustable by chemically modified, the response fast, flexible, easily be processed into large area flexible device and advantage cheap and easy to get.The key issue that organic solar batteries faces is poor efficiency and short life.
From the material angle, inefficient major cause has 2 points: it is not wide that organic semiconductor material absorbs the sunlight wave band, overwhelming majority material maximum absorption wave band is at 350-650nm, and sunlight maximum photon stream is at 600-800nm, therefore absorption spectrum and sun emmission spectrum do not match, and the sunlight utilization ratio is low.At present, there are many organic semiconductor material to be developed, wherein with pentacene, thiophene-based, C 60The most representative with phthalocyanine pigment, wherein, (1) this two classes material of pentacene and Uniformpoly thiophene has narrower energy gap and higher H OMO track, in air, easily have an effect, so the organic photovoltaic devices that makes with this type of material is stable bad (referring to Torsi L, Cioffi N with oxygen, water, Franco C D, et al.Solid-StateElectrons, 2001,45:1480; ); (2) C 60Bad with the solvability of phthalocyanine pigment, influence its processing characteristics (referring to the triumph of: road, Liu is wide, Yang Mujie. polymer material science and engineering, 2005,21 (4): 1-4; The Zhang Yun crane, Niu Yaming, the academic paper report of .2005 such as Wang honored guest whole nation polymer, minutes ID:6334854); Next is the energy gap width part of corresponding solar spectrum only of these materials, thereby can only absorb a part of sunlight, can not effectively utilize the full spectrum of sun power (referring to: the Li Li osmanthus wide vast and boundless Yang Xiaoniu in Shandong etc. Science Bulletin, 2006,51 (21): 2458-2468).The organic photosensitive material that searching spectral response and sunlight are complementary just becomes a focus of present research and solves a low breach of organic photovoltaic battery transformation efficiency.
Summary of the invention
The object of the invention provides a kind of triphenylamine-two thieno-indene derivative with photovoltaic property.
For achieving the above object, the technical solution used in the present invention is: a kind of triphenylamine-two thieno-indene derivative with photovoltaic property, and the general formula of described triphenylamine-two thieno-indene derivative is as follows:
Figure GSA00000034175600021
Wherein, D represents electronic donor group, and particularly, D is a kind of of following group:
(1) contain the vinyl of 1 trianilino group:
Figure GSA00000034175600022
(2) contain the vinyl of 3 trianilino groups:
Figure GSA00000034175600023
(3) contain the styryl of 1 trianilino group:
(4) contain the styryl of 1 trianilino group:
Figure GSA00000034175600032
Corresponding, the structural formula of described triphenylamine-two thieno-indene derivative is as follows:
(1) compd A:
Figure GSA00000034175600033
(2) compd B:
Figure GSA00000034175600034
(3) Compound C:
Figure GSA00000034175600041
(4) Compound D:
Figure GSA00000034175600042
In the technique scheme, triphenylamine-two thieno-indene derivative is molecule " nuclear " with the fluoro-substituted indene, has the electronic property of drawing (A), 4 of indenes ring, 5 and 6,7 condense with thiphene ring respectively, the sulphur atom ortho position is connected the electron donor(ED) (D) that contains the triphen amido, constitutes " D '-A-D ' " type conjugated molecule, its general formula is:
Figure GSA00000034175600043
Further four kinds of triphenylamine-two thieno-indene derivatives described in the technique scheme are studied, are found:
(1) four kinds of triphenylamine-two thieno-indene derivatives have the strong absorbing band of wide band described in the technique scheme, the absorption spectrum of its molecule in solution and solid film all has obvious absorption at 200～850nm wave band, peak position is distributed in about 200nm, about 400nm and Fig. 2 (sees in about 700nm place, Fig. 3), have overlapping preferably with the full spectrum of the sun.
(2) four kinds of triphenylamine-two thieno-indene derivative molecular materials present tangible fluorine atom substituting effect described in the technique scheme, make compd A, compd B and Compound C show n-N-type semiconductorN feature and (see Fig. 4,5), its HOMO energy level is about that 4.0eV, lumo energy are about 5.6eV, band gap is about 1.6eV.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. be strong electron donor(ED) owing to the present invention selects trianilino group, promoted the closed (see figure 1) of photosensitive di-thiofuran ethylene group, obtain four kinds of good condensing of photostability " indenes " derivative, has the strong absorbing band of wide band, the absorption spectrum of its molecule in solution and solid film all has obvious absorption at 200～850nm wave band, peak position is distributed in～200nm ,～400nm and～the 700nm place (sees Fig. 2, Fig. 3), have overlappingly preferably with the full spectrum of the sun, can effectively utilize the full spectrum of sun power.
2. most organic semiconductors are p-N-type semiconductorN character, the spectral range that is covered is higher than 1.8eV, molecular material of the present invention presents tangible fluorine atom substituting effect, make compd A, compd B and Compound C show n-N-type semiconductorN feature and (see Fig. 4,5), its HOMO energy level is about that 4.0eV, lumo energy are about 5.6eV, band gap is about 1.6eV.
3. use the heterojunction photovolatic cell that gained of the present invention four kinds of triphenylamines-two thieno-indene derivative and P3HT (p-N-type semiconductorN) or PCBM (n-N-type semiconductorN) constitute, open circuit voltage (Voc) is 0.8V, short-circuit photocurrent density (J to the maximum Sc) maximum 1.18mAcm -2(seeing Table 1, Fig. 6,7).
Description of drawings
Fig. 1 is that forceful electric power that contains trianilino group among the embodiment one to four has promoted " indenes " ring to form synoptic diagram to volume property;
Fig. 2 is the absorption spectrum in each comfortable acetonitrile solution of embodiment one to four gained compound;
Fig. 3 is each auto-doping PMMA film absorption spectrum of embodiment one to four gained compound;
Fig. 4 is the cyclic voltammetric CV curve of embodiment one to four gained compound;
Fig. 5 is embodiment one to four gained compound, P3HT (p-N-type semiconductorN), PCBM (n-N-type semiconductorN) molecular entergy level figure;
Fig. 6 is that (wherein, active coating composition: compd A and P3HT mixed the test area of device: 0.1cm by 1: 1 to device architecture and organic photovoltaic performance map among the embodiment nine 2, sunlight intensity: AM1.5:100mW/cm 2);
Fig. 7 is that (wherein, active coating composition: Compound D and PCBM mixed the test area of device: 0.09cm by 1: 1 to device architecture and organic photovoltaic performance map among the embodiment nine 2, sunlight intensity: AM1.5:100mW/cm 2).
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: (E)-2, and 2 '-two [(4,4-diphenylamino styryl)]-1,1,2,2,3,3-hexafluoro--5.6-dimethyl-4,5,6,7-two thieno-indenes synthetic.
Synthetic route is as shown below:
Figure GSA00000034175600061
Concrete steps are as follows:
[1] 5-methyl-4-bromo-2 thiophene carboxaldehyde (compound (2)) is synthetic: under ice bath and agitation condition, the mixed solution of bromine (3mL) and glacial acetic acid (8mL) is packed in the constant pressure funnel, slowly drop to then and fill 2-methyl-5-aldehyde radical-thiophene (compound 1,6.3g, in the there-necked flask of glacial acetic acid 50mmol) (35mL) solution, dropwise the back and continue reaction 5h, add water (40mL) stopped reaction.Reaction solution Na 2CO 3Neutralization is after chloroform extraction three times, merge organic phase, concentrated solution separates (ethyl acetate: sherwood oil moving phase) collect weak yellow liquid through post, for compound (2) (4.8g, 23.4mmol), (account form of productive rate is: with theoretical reaction yield is 100% to productive rate 44.0%, amount with initial compounds, theory of computation maximum production, the amount according to actual product obtains productive rate divided by theoretical yield then, down together).
[2] 1,2-is two, and [(the 5-methyl-[2-(2,5 dioxolane)]-and the 4-thienyl] hexafluoro cyclopentenes (compound (4)) synthetic: respectively with compound (2) (4.8g, 23.4mmol), ethylene glycol 6mL, p-methyl benzenesulfonic acid 0.09g joins in the 200mL benzene, reflux 12h under the Dean-Stark condition, TLC follows the tracks of.Reaction stops the back decompression and removes benzene, collects light brown liquid (compound (3)) through decompression again, carries out next step reaction.
In nitrogen protection ,-78 ℃ under condition, (5.246g 21.06mmol) is dissolved among the refining THF and stirs, and (2.72M, 21.06mmoL), C reinjects to inject n-Butyl Lithium with compound (3) 5F 8(10mL), keep this temperature stirring reaction 2h, rise to room temperature naturally, add the water stopped reaction, organic phase behind separatory is with saturated common salt water washing 3 times, anhydrous magnesium sulfate drying, cross post separate compound (4), brown dope (2.210g, 4.31mmol), productive rate 43.0%.
[3] 1, synthesizing of two [(5-methyl-2-aldehyde radical)-4-thienyl] the hexafluoro cyclopentenes (compound (5)) of 2-: in round-bottomed flask, add compound 4 (2.210g successively, 4.31mmol), p-methyl benzenesulfonic acid 0.100g, 2 of pyridines, acetone 50mL and 10mL water, reflux gets 1.646g (3.88mmol) compound 5, pale yellow powder, productive rate 90%.
[4] (E)-2,2 '-two [(4,4-diphenylamino styryl)]-1,1,2,2,3,3-hexafluoro--5.6-dimethyl-4,5,6,7-two thieno-indenes (compd A) synthetic: with compound (5) (0.100g, 0.236mmol) and triphenylamine quaternary alkylphosphonium salt 0.438g, dioxane 30mL, NaH 0.038g, reflux 48h, TLC follows the tracks of, and after reaction stops, after the cooling reaction soln being concentrated, pour in the water, neutralization back crude product is crossed post and is got blackish green powder, productive rate 32%.
Analyze the gained compound:
Mass spectrum (MALDI-TOF-TOF) measured value: 906.3, calculated value (906.25);
1H?NMR(400MHz，CDCl 3，TMS)：δ2.17(s，6H，-CH3)，6.32(s，2H，thiophene-H)，6.67，6.71(d，4H，C＝C-H)，6.96-7.00(m，4H，benzene-H)，7.08-7.14(m，12H，benzene-H)，7.26-7.32(m，12H，benzene-H)；
The molecular formula of the compd A that obtains is:
Embodiment two: (E)-2, and 2 '-two [(4,4-diphenylamino diphenylethyllene)]-1,1,2,2,3,3-hexafluoro--5.6-dimethyl-4,5,6,7-two thieno-indenes synthetic.
Adopt with embodiment one in identical method obtain compound (5), Wittig (Wittig) reaction compound (5) and methyl iodide is taken place under triphenyl phosphorus catalysis again, the dioxane solvent, refluxing obtained 1 in 6 hours, two [(5-methyl-2-vinyl)-4-thienyl] the hexafluoro cyclopentenes (compound (7)) of 2-.Mass spectrum (MALDI-TOF-TOF) measured value: 420.04, calculated value (420.045).
Figure GSA00000034175600081
Under the anhydrous and oxygen-free condition, compound (7) and 4,4 '-two-(diphenyl amino-diphenylethyllene)-amino-benzene ethene (compound (8), referring to: application number is 2007100202855 Chinese invention patent Shen Qing Publication specification sheets) reaction in 1: 2.2 in molar ratio.Triethylamine: acetonitrile (1: 8) mixed solvent, adjacent methyl triphenyl phosphine and palladium are made catalyzer and are added in the 100ml there-necked flask, 85 ℃ of back flow reaction 24h, the cooling back concentrates, with ethyl acetate: sherwood oil=5: 1 is the elutriant column chromatography for separation, get compd B, blackish green powder, productive rate 20.2%.
Mass spectrum (MALDI-TOF-TOF) measured value: 2134.8, calculated value (2134.8);
1H?NMR(400MHz，CDCl 3，TMS)：δ2.19(s，6H，-CH 3)，6.35(s，2H，thiophene-H)，6.69，6.73(d，12H，C＝C-H)，6.97-7.01(m，8H，benzene-H)，7.08-7.15(m，36H，benzene-H)，7.27-7.33(m，20H，benzene-H)，7.08-7.15(m，16H，benzene-H)；
The molecular formula of the compd B that obtains is:
Figure GSA00000034175600082
Embodiment three: (E)-2, and 2 '-two { 4,4 '-two [4,4 '-two (diphenylamino-diphenylethyllene) amino]-vinylbenzene }-1,1,2,2,3,3-hexafluoro--5.6-dimethyl-4,5,6,7-two thieno-indenes synthetic.
Figure GSA00000034175600091
[1] 2-methyl-3,5-two bromo-thiophene (compound (10)) are synthetic: under ice bath and agitation condition, with bromine/glacial acetic acid (V/V, mixed solution 29mL/40mL) is packed in the constant pressure funnel, slowly drop to then fill 2-methyl-thiophene (compound (9), 24g is in the there-necked flask of glacial acetic acid 244.8mmol) (100mL) solution, dropwise the back and continue reaction 5h, add water (40mL) stopped reaction.Reaction solution Na 2CO 3Neutralization is after extracted with diethyl ether three times merges organic phase, drying, filtration, concentrates after colourless liquid is collected in underpressure distillation, is compound 10, productive rate 78.4%. 1H?NMR(400MHz，CDCl 3)：δ2.94(s，3H)，7.61(s，1H)；IR(v，cm -1)：780，810，950，1010，1139，1302，1451，1536，2786，and?3081.
[2] 3-bromo-2-methyl-5-thienyl boric acid ester (compound (11)) is synthetic: under-78 ℃ of nitrogen protection; toward filling compound (10) (16.3g; 63.7mmol) dry diethyl ether (150mL) in, inject n-Butyl Lithium hexane solution (1.6mol/L, 40.6mL; 65.0mmol); stirring reaction is after half an hour, injects 18.8mL boric acid three n-butyl, treat temperature nature appreciation room temperature after; (4%, 10mL) cancellation is reacted to add dilute hydrochloric acid.Neutralize through 10%HCl again through the extractive product solution of diluted alkaline (4%NaOH 100mL).After washing, filtration, drying, obtain faint yellow solid, productive rate 70%. 1H?NMR(400MHz，CDCl3，TMS)：δ2.51(s，3H)，4.59(s，2H)，7.33(s，1H)；IR(v，cm -1)：690，790，832，1010，1132，1340，1474，1528，1291，3202.
[3] 2-methyl-3-bromo-5-(4-bromo phenyl) thiophene (compound (12)) is synthetic: with compound (11) (2.4g, 10.7mmol) and 1, the 4-dibromobenzene (2.5g, 10.7mmol), Pd (PPh 3) 4(0.3g) and yellow soda ash (4.2g 40mmol) joins in the there-necked flask, and (100mL contains 10%H to add THF again 2O), back flow reaction 16h. cooling back merges organic phase with extracted with diethyl ether three times, dry, filter, concentrate after, through column chromatography purify yellow powder, productive rate 60%.Mass spectrum (MALDI-TOF-TOF) measured value: 329.9, calculated value (329.9).
[4] (E)-1, two [2-(4-bromophenyl)-5-methyl-4-thienyl] the hexafluoro cyclopentenes (compound (13)) of 2-is synthetic.In nitrogen protection ,-78 ℃ under condition, compound (12) (21.06mmol) is dissolved among the refining THF and stirs, (2.72M, 21.06mmoL), C reinjects to inject n-Butyl Lithium 5F 8(10mL), keep this temperature stirring reaction 2h, rise to room temperature naturally, add the water stopped reaction, organic phase behind separatory is with saturated common salt water washing 3 times, anhydrous magnesium sulfate drying, cross post separate yellow solid, productive rate 40.0%.Mass spectrum (MALDI-TOF-TOF) measured value: 675.9, calculated value (679.9).
[5] (E)-2,2 '-two { 4,4 '-two [4,4 '-two (diphenylamino-diphenylethyllene) amino]-vinylbenzene }-1,1,2,2,3,3-hexafluoro--5.6-dimethyl-4,5,6, synthesizing of 7-two thieno-indenes (Compound C): under the anhydrous and oxygen-free condition, compound (13) and 4-N, N-diphenyl amino styryl (compound (14)) reaction in 1: 2.2 in molar ratio.10mL triethylamine and 8mL acetonitrile are made solvent, and adjacent methyl triphenyl phosphine of 0.0162g and 0.0048g palladium are made catalyzer and added in the 100mL there-necked flask, 85 ℃ of back flow reaction 24h, and the cooling back concentrates, and gets blackish green powder through column chromatography for separation, productive rate 24%.
Analyze the gained compound:
Mass spectrum (MALDI-TOF-TOF) measured value: 2134.8, calculated value (2134.8);
1H?NMR(400MHz，CDCl 3，TMS)：δ2.18(s，6H，-CH 3)，6.69(s，2H，thiophene-H)，7.01-7.03(m，12H，benzene-H)，7.11-7.13(m，16H，C＝C-H，benzene-H)，7.25-7.29(m，12H，benzene-H)，7.39，7.41(m，4H，J＝8.0，benzene-H)，7.52，7.54(d，8H，J＝8.0，benzene-H).
13C?NMR(100MHz，CDCl 3，TMS)：δ29.66，123.18，123.30，124.58，124.75，125.71，126.50，127.28，127.64，129.32，147.43.
The molecular formula of the Compound C that obtains is:
Figure GSA00000034175600101
Embodiment four: (E)-2, and 2 '-two { 4,4 '-two [4,4 '-two (diphenylamino-diphenylethyllene) amino]-vinylbenzene }-1,1,2,2,3,3-hexafluoro--5.6-dimethyl-4,5,6,7-two thieno-indenes synthetic.
Similar method among employing and the embodiment three, only need to change compound (14) into 4 according to the compound that obtains, 4 '-two-(diphenyl amino-diphenylethyllene)-amino-benzene ethene (compound (15), be called for short G2-branch, its preparation method is referring to Zezhu Huang, Xiaomei Wang et al.Optical Materials, 2007,29:1084-1090), the structural formula of compound (15) is:
Figure GSA00000034175600111
Analyze gained embodiment (14) compound: blackish green, productive rate 26%.
Mass spectrum (MALDI-TOF-TOF) measured value: 2134.8, calculated value (2134.8);
1H?NMR(400MHz，CDCl 3，TMS)：δ2.18(s，6H，-CH 3)，6.69(s，2H，thiophene-H)，7.01-7.03(m，12H，benzene-H)，7.11-7.13(m，16H，C＝C-H，benzene-H)，7.25-7.29(m，12H，benzene-H)，7.39，7.41(m，4H，J＝8.0，benzene-H)，7.52，7.54(d，8H，J＝8.0，benzene-H).
The Compound D molecular formula that obtains is:
Figure GSA00000034175600112
Selecting trianilino group among the embodiment one to four is strong electron donor(ED), has promoted the closure (referring to Fig. 1) of photosensitive di-thiofuran ethylene group.
Embodiment five, and embodiment one to four gained compd A, compd B, Compound C and Compound D are dissolved in acetonitrile respectively, and being mixed with concentration is 2.0 * 10 -5The solution of M, (absorption spectrum is measured on UV-Vis Tu-1800spc ultraviolet spectrometer, and cuvette thickness 1cm tests solvent for use through distillation again to test its corresponding absorption spectrum.)
The result is referring to Fig. 2, as shown in Figure 2, compd A, compd B, Compound C and Compound D have the strong absorbing band of wide band, the absorption spectrum of its molecule in solution all has obvious absorption at 200～850nm wave band, peak position is distributed in～200nm ,～400nm and～700nm place and the full spectrum of the sun have overlapping preferably.
Embodiment six, with embodiment one to four gained compd A, compd B, Compound C and Compound D respectively with the PMMA polymkeric substance, mix according to prior art, formation contains the PMMA film of mass percent 10% respective compound, (absorption spectrum is measured on UV-Vis Tu-1800spc ultraviolet spectrometer to test its corresponding absorption spectrum, cuvette thickness 1cm, the test solvent for use is through distillation again.)
The result is referring to Fig. 3, as shown in Figure 3, compd A, compd B, Compound C and Compound D have the strong absorbing band of wide band, the absorption spectrum of its molecule in the PMMA film all has obvious absorption at 200～850nm wave band, peak position is distributed in～200nm ,～400nm and～700nm place and the full spectrum of the sun have overlapping preferably.
Embodiment seven, record the cyclic voltammetry curve of embodiment one to four gained compd A, compd B, Compound C and Compound D.
Make solvent with methylene dichloride under the room temperature, supporting electrolyte is tetrabutyl ammonium hexafluorophosphate (n-Bu 4NPF 6, commodity) and make ionogen, under nitrogen protection, adopt the cyclic voltammetric characteristic of CHI 601B type electrochemistry work system working sample, concentration is 0.05moldm during measurement -3, adopting three-electrode system, counter electrode is a platinum wire electrode, and working electrode is a glass-carbon electrode, and reference electrode is the Ag/AgCl electrode, and working electrode economy-combat grinding and polishing light before experiment cleans.Feed high pure nitrogen 10min before the experiment to remove dissolved oxygen in the solution, and in experimentation, continue to feed nitrogen, scanning speed is 50mv/s), the result is referring to Fig. 4, as shown in Figure 4, Fig. 4 provides cyclic voltammetric (CV) curve of compd A-D, and as can be known: compd A, B, C and the D first oxidation peak position are respectively 0.75V, 0.91V, 0.86V and 0.96V.Show that by compd A to compd B, along with triphenylamine " branch " algebraically increases, molecular change must be difficult for losing electronics, anode spike potential raise (to Compound D also in this way) by Compound C.After inserting phenyl ring between two thieno-indenes " nuclear " and the triphenylamine " branch ", as getting structure by the compd A structure to Compound C, molecule also becomes and is difficult for losing electronics, anode spike potential rising (by compd B to Compound D also in this way).Calculate HOMO, energy level is respectively :-5.49eV (compd A) ,-5.64eV (compd B) ,-5.61eV (Compound C) and-5.69eV (Compound D).
Embodiment eight, and (concrete grammar is referring to P.Herguth, X.Z.Jiang to obtain the molecular entergy level data of embodiment one to four gained compound by ultraviolet spectrum data and electrochemical data, M.S.Liu et al, Macromolecules, 2002,35:6094-6100).
Fig. 5 is embodiment one to four, poly-3-hexyl thiophene (P3HT, poly (3-hexyl thiophene)) (p-N-type semiconductorN), 6,6-phenyl-C61 methyl-butyrate (PCBM, [6,6]-phenyl C61 butyricacid methyl ester) (n-N-type semiconductorN) molecular entergy level figure, among the figure 1,2,3,4 are respectively embodiment 1, embodiment 2, embodiment 3 and embodiment 4 gained compd As, compd B, Compound C and Compound D.As shown in Figure 5: compd A, compd B and Compound C show n-N-type semiconductorN feature, and its HOMO energy level is about that 4.0eV, lumo energy are about 5.6eV, band gap is about 1.6eV.
Embodiment nine, as shown in Figure 6, according to prior art (referring to Shi Minmin, Chen Hongzheng, Wang is boundless and indistinct, solar energy journal, 2006,27 (6): 525-529) preparation active coating composition: compd A and P3HT mixed by 1: 1, comprising: the heterojunction photovolatic cell of glass substrate (Glass)/ITO electrode/PEDOT/POSS/ active coating/LiF/Al electrode, the test area of the organic battery device of gained: 0.1cm 2, sunlight intensity: AM1.5:100mW/cm 2, test its organic photovoltaic performance.
As shown in Figure 7, according to prior art for preparing active coating composition: Compound D and PCBM mixed by 1: 1, comprise: the heterojunction photovolatic cell of glass substrate (Glass)/ITO electrode/PEDOT/POSS/ active coating/LiF/Al electrode, the test area of the organic battery device of gained: 0.1cm 2, sunlight intensity: AM1.5:100mW/cm 2, test its organic photovoltaic performance.
The method that compd B, C prepare heterojunction photovolatic cell is identical with Compound D.
The result is referring to table 1 and Fig. 6,7.
Table 1 contains the photovoltaic character of the heterojunction active coating of embodiment one to four
The heterojunction active coating (1/1, w/w) Short-circuit current density (J SC/mA?cm -2) Open circuit voltage (V OC/mV) Packing factor (FF) Efficient (η/%)
Compd A: P3HT ??1.18 ??740 ??0.26 ??0.23
Compd B: PCBM ??0.42 ??500 ??0.25 ??0.06
Compound C: PCBM ??0.51 ??800 ??0.25 ??0.10
Compound D: PCBM ??0.94 ??640 ??0.31 ??0.18
Photronic negative electrode is: LiF/Al, anode are the ITO that PEDOT/POSS modifies.

Claims (1)

1. triphenylamine-two thieno-indene derivative with photovoltaic property is characterized in that the general formula of described triphenylamine-two thieno-indene derivative is as follows:
Figure FSA00000034175500011
Wherein, D represents electronic donor group, and particularly, D is a kind of of following group:
Figure FSA00000034175500012
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CN102702145A (en) * 2012-06-01 2012-10-03 吉林大学 Triphenylamine derivative, preparation method and application thereof in dye sensitization solar cell
CN103130846A (en) * 2012-11-27 2013-06-05 江西科技师范大学 Photochromic bi-thiophene six-sugar water-solubility symmetrical octafluorocyclopentene compound and preparation method and application

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《功能材料》 20081231 周懋怡等 硫杂芴－三苯胺树枝形分子的合成与电致发光特性研究 1420－1422 1 第39卷, 第9期 2 *
《高等学校化学学报》 20080831 张唯舟等 氧芴三苯胺多枝分子的双光子吸收与电化学行为 1616－1619 1 第29卷, 第8期 2 *

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Publication number Priority date Publication date Assignee Title
CN102702145A (en) * 2012-06-01 2012-10-03 吉林大学 Triphenylamine derivative, preparation method and application thereof in dye sensitization solar cell
CN102702145B (en) * 2012-06-01 2014-04-09 吉林大学 Triphenylamine derivative, preparation method and application thereof in dye sensitization solar cell
CN103130846A (en) * 2012-11-27 2013-06-05 江西科技师范大学 Photochromic bi-thiophene six-sugar water-solubility symmetrical octafluorocyclopentene compound and preparation method and application

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