CN103159925A - Isoindigo based co-polymer solar cell material, and preparation method and application thereof - Google Patents
Isoindigo based co-polymer solar cell material, and preparation method and application thereof Download PDFInfo
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- CN103159925A CN103159925A CN2011104097958A CN201110409795A CN103159925A CN 103159925 A CN103159925 A CN 103159925A CN 2011104097958 A CN2011104097958 A CN 2011104097958A CN 201110409795 A CN201110409795 A CN 201110409795A CN 103159925 A CN103159925 A CN 103159925A
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- MLCPSWPIYHDOKG-BUHFOSPRSA-N (3e)-3-(2-oxo-1h-indol-3-ylidene)-1h-indol-2-one Chemical compound O=C\1NC2=CC=CC=C2C/1=C1/C2=CC=CC=C2NC1=O MLCPSWPIYHDOKG-BUHFOSPRSA-N 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 61
- 229920001577 copolymer Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 52
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 29
- 229910052763 palladium Inorganic materials 0.000 claims description 26
- 238000006619 Stille reaction Methods 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 5
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 claims description 5
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 5
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 2
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 abstract 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- 238000005804 alkylation reaction Methods 0.000 abstract 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 125000005605 benzo group Chemical group 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000000638 solvent extraction Methods 0.000 description 7
- 229930192474 thiophene Natural products 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 125000006608 n-octyloxy group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 0 C*c1c2[s]c([Sn](C)(C)C)cc2c(C=O)c([s]2)c1cc2[Sn](C)(C)C Chemical compound C*c1c2[s]c([Sn](C)(C)C)cc2c(C=O)c([s]2)c1cc2[Sn](C)(C)C 0.000 description 3
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 3
- WOUIKYKNZGCTCD-UHFFFAOYSA-N [O].CCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCC WOUIKYKNZGCTCD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- -1 dodecyl isoindigo Chemical compound 0.000 description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- VIMCPPVWFHVVAX-ISLYRVAYSA-N CN(c1cc([Br]=C)ccc1/C1=C(/c(c(N2C)c3)ccc3[Br]=C)\C2=O)C1=O Chemical compound CN(c1cc([Br]=C)ccc1/C1=C(/c(c(N2C)c3)ccc3[Br]=C)\C2=O)C1=O VIMCPPVWFHVVAX-ISLYRVAYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- NSLJAYQJTGJPBW-UHFFFAOYSA-N S1C=CC2=C1C=CS2.C2=CC=CC=C2 Chemical compound S1C=CC2=C1C=CS2.C2=CC=CC=C2 NSLJAYQJTGJPBW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention belongs to the field of solar cells, and discloses an isoindigo based co-polymer solar cell material, and a preparation method and an application thereof. The co-polymer has the following structural formula (I). In the formula, both R1 and R2 represent a C1-C20 alkyl group and n is an integer ranging from 10 to 100. In the isoindigo based co-polymer solar cell material provided by the invention, benzo-dithiophene has easily modified photophysical properties, and the co-polymer of the benzo-dithiophene presents excellent photovoltaic performance; isoindigo contains centrosymmetric pyrrolidone cores, so that an alkylation reaction of N atoms becomes very easily, and solubility property and photoelectric properties of the polymer can be adjusted by adjusting groups on the N atoms. Besides, isoindigo has two carbonyl groups with relatively strong electron-withdrawing effect, so that an HOMO energy level and a LUMO energy level can be reduced, thereby facilitating the increase of an open-circuit voltage. The performance can improve energy conversion efficiency of solar energy, so that the problem of low efficiency of polymer solar cells is solved.
Description
Technical field
The present invention relates to the solar cell material field, relate in particular to a kind of isoindigo base co-polymer solar cell material and its preparation method and application.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.The silicon wafer battery that is used for ground at present is restricted its application because complex manufacturing, cost are high.In order to reduce the battery cost, expand range of application, people are seeking novel solar cell material always for a long time.Organic semiconductor material with its raw material be easy to get, cheap, preparation technology is simple, environmental stability good, have the good advantages such as photovoltaic effect to receive much concern.From N.S.Sariciftci in 1992 etc. at SCIENCE (N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C
60Between the Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed, but still much lower than the efficiency of conversion of inorganic solar cell.
Summary of the invention
The isoindigo base co-polymer solar cell material that provides a kind of effciency of energy transfer high is provided purpose one of the present invention.
A kind of isoindigo base co-polymer solar cell material with following structural formula (I):
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer, preferred n is 50～70.
Another object of the present invention is to provide the preparation method of above-mentioned isoindigo base co-polymer solar cell material, comprise the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
A：
B：
Wherein, in described compd A, R
1Be C
1～C
20Alkyl; In described compd B, R
2Be C
1～C
20Alkyl;
S2, under oxygen-free environment, with described compd A and compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer, fully after the dissolving after carrying out Stille coupling reaction 12～96h under 70～130 ℃, obtain having following structural formula after the cooling stopped reaction described isoindigo base co-polymer solar cell material of (I):
In formula, n is the integer of 10-100.
In the preparation method of above-mentioned isoindigo base co-polymer solar cell material, in described step S2:
Described catalyzer is organic palladium, and described organic palladium is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; The mol ratio of described organic palladium and described compd A is 1: 20～1: 100; Perhaps
Described catalyzer be organic palladium (as, three dibenzalacetone two palladiums) with organophosphor ligand (as, tri-butyl phosphine) mixture, in this mixture, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8.
Described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF);
The preparation method of described isoindigo base co-polymer solar cell material, preferably, in described step S2:
Described Stille coupling reaction temperature is 80～110 ℃; The described Stille coupling reaction time is 24～72h.
Another purpose of the present invention is to provide the application of above-mentioned isoindigo base co-polymer solar cell material in the organic solar batteries active coating.
Isoindigo base co-polymer solar cell material provided by the invention, benzo two thiophene have the photophysical property of easy modification, and its co-polymer has demonstrated good photovoltaic performance; Isoindigo is to contain centrosymmetric pyrrolidone core, and the alkylated reaction on N becomes and is very easy to carry out, by regulating solubility property and the photoelectric properties that group on N can telomerized polymer.In addition, it also has two carbonyls of strong sucting electronic effect, thereby causes HOMO and lumo energy to reduce, and is conducive to like this raising of open circuit voltage.This performance can improve the effciency of energy transfer of sun power, thereby solves the polymer solar battery low efficiency problem.。
In addition, in the preparation method of above-mentioned isoindigo base co-polymer, adopted better simply synthetic route, thereby reduced technical process, material is cheap and easy to get, reduces manufacturing cost, and the material structure that makes is novel, and solubility property is good, and film forming properties is good.
Description of drawings
Fig. 1 is preparation technology's schema that the present invention contains isoindigo base co-polymer solar cell material;
Fig. 2 is the effciency of energy transfer graphic representation of the multipolymer of embodiment 1 preparation;
Fig. 3 is the organic solar energy cell structure schematic diagram of embodiment 7.
Embodiment
The isoindigo base co-polymer solar cell material with following structural formula (I) that present embodiment provides:
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer; N is preferably 50～70.
The preparation method of above-mentioned isoindigo base co-polymer solar cell material as shown in Figure 1, comprises the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
A：
2,6-, two tin trimethyls-4,8-dialkoxy benzene 1,4-Dithiapentalene;
B：
6,6 '-two bromo-N, N '-dialkyl group isoindigo;
Wherein, in compd A, R
1Be C
1～C
20Alkyl; In compd B, R
2Be C
1～C
20Alkyl;
S2, oxygen-free environment (as, the oxygen-free environment that nitrogen, argon gas or nitrogen and argon gas gas mixture etc. consist of) under, with described compd A and compd B according to 1: 1 add-on of mol ratio, be added into and contain in the catalyzer organic solvent, fully dissolving is rear after carrying out Stille coupling reaction 12～96h under 70～130 ℃, obtain mixed solution after the cooling stopped reaction, comprise product in this mixed solution, namely have the described isoindigo base co-polymer solar cell material of following structural formula (I):
In formula, n is 10～100 integer;
S3, the product in step S2 is carried out purification process:
Add methyl alcohol in the mixed solution of step S2, carry out precipitating and process, filter with apparatus,Soxhlet's subsequently, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourlessly as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after 50 ℃ of dry 24h under vacuum, is obtained the isoindigo base co-polymer solar cell material of purifying.
In the preparation method of above-mentioned isoindigo base co-polymer solar cell material, in described step S2:
Described catalyzer is organic palladium, and described organic palladium is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; The mol ratio of described organic palladium and described compd A is 1: 20～1: 100; Perhaps
Described catalyzer be organic palladium (as, three dibenzalacetone two palladiums) with organophosphor ligand (as, tri-butyl phosphine) mixture, in this mixture, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8.
Described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF);
The preparation method of described isoindigo base co-polymer solar cell material, preferably, in described step S2:
Described Stille coupling reaction temperature is 80～110 ℃; The described Stille coupling reaction time is 24～72h.
Above-mentioned isoindigo base co-polymer solar cell material can be used as the organic solar batteries active layer material, is mainly the electron donor material in active coating.
In order to understand better the content of patent of the present invention, further illustrate technology case of the present invention below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein, but the monomer reference literature (Chem.Mater. of compd A, 2008,20,7510) the synthetic purchase from the market of disclosed method obtains, but monomer reference literature (Org.Lett., 2010 of compd B, 12,660) disclosed method is synthetic or buy from the market and obtain.
Embodiment 1
The isoindigo base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,8-two (n-octyloxy) benzo, two thiophene-co-N, N '-di-n-octyl isoindigo }, wherein, R
1Be octane base, R
2Be the octane base, n is 60, and its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
With 2,6-two tin trimethyls-4,8-two (n-octyloxy) benzo two thiophene (232mg, 0.3mmol), 6,6 '-two bromo-N, N '-di-n-octyl isoindigo (193mg, 0.3mmol), three dibenzalacetone two palladium (13.75mg, 0.015mmol), tri-butyl phosphine (24.2mg, 0.12mmol) add in the flask that fills 12mL toluene, then logical nitrogen purge gas approximately after 30min, stir under 95 ℃, Stille coupling reaction 40h, stop polyreaction after cooling, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is under vacuum after 50 ℃ of dry 24h, be poly-{ 4,8-two (n-octyloxy) benzo two thiophene-co-N, N '-di-n-octyl isoindigo } product, productive rate is 75%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=55.8kDa, M
w/ M
n=2.2.
Fig. 2 is the effciency of energy transfer graphic representation of the multipolymer of embodiment 1 preparation; Result shows, at AM1.5; 100mW/cm
2Under illumination, the effciency of energy transfer that is the body heterojunction solar cell of donor material based on the polymkeric substance of embodiment 1 is 4.2%; Mei etc. have reported take the isoindigo base co-polymer as donor material, and PCBM is that acceptor material has prepared solar cell, and effciency of energy transfer is 2.4%.(Organic?Letters?2010，12，660)。
The isoindigo base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,8-two (methoxyl group) benzo, two thiophene-co-N, N '-two (NSC 62789 base) isoindigo }, wherein, R
1Be methyl, R
2Be the NSC 62789 base, n is 40, and its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
With 2,6-two tin trimethyls-4,8-two (methoxyl group) benzo two thiophene (115mg, 0.2mmol), 6,6 '-two bromo-N, N '-two (eicosyl) isoindigo (196mg, 0.2mmol) add in the flask of the DMF solvent that fills 15ml, be dissolved into solution, the evacuated flask deoxygenation also is filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol), stirring, Stille coupling reaction 24h under 120 ℃, stop polyreaction after cooling, obtain mixed solution.
Add 50mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 4 after 50 ℃ of dry 24h under vacuum, 8-two (methoxyl group) benzo two thiophene-co-N, N '-two (NSC 62789 base) isoindigo } product, productive rate 70%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=42.8kDa, M
w/ M
n=2.3.
Embodiment 3
The isoindigo base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,8-two (NSC 62789 oxygen base) benzo two thiophene-co-N, N '-dimethyl isoindigo }, wherein, R
1Be NSC 62789 base, R
2Be methyl, n is 80, and its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
with 2,6-two tin trimethyls-4,8-two (NSC 62789 oxygen base) benzo two thiophene (333mg, 0.3mmol) and 6,6 '-two bromo-N, N '-dimethyl isoindigo (134mg, 0.3mmol) add in the two-mouth bottle of the 50mL specification that fills the 15mL tetrahydrofuran (THF), be dissolved into solution, logical nitrogen and argon gas gas mixture, air-discharging is approximately after 20min, then with tetra-triphenylphosphine palladium (4mg, 0.003mmol) add in two-mouth bottle, fully lead to again nitrogen and argon gas gas mixture, continue air-discharging approximately after 10min, stir under 80 ℃, Stille coupling reaction 72h, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 4 after 50 ℃ of dry 24h under vacuum, 8-two (NSC 62789 oxygen base) benzo two thiophene-co-N, N '-dimethyl isoindigo } product, productive rate is 73%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=85.6kDa, M
w/ M
n=2.2.
The isoindigo base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,8-(n-butoxy) benzo, two thiophene-co-N, N '-two (n-decane base) isoindigo }, wherein, R
1Be normal-butyl, R
2Be the n-decane base, n is 100, and its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
With 2,6-two tin trimethyls-4,8-two (n-butoxy) benzo two thiophene (132mg, 0.2mmol), 6,6 '-two bromo-N, N '-two (n-decane base) isoindigo (140mg, 0.2mmol) add in the flask of the tetrahydrofuran solvent that fills 15ml, be dissolved into solution, the evacuated flask deoxygenation also is filled with argon gas, then adds bi triphenyl phosphine dichloride palladium (7.2mg, 0.01mmol), stirring, Stille coupling reaction 96h, stop polyreaction after cooling under 70 ℃, obtains mixed solution.
Add 50mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 4 after 50 ℃ of dry 24h under vacuum, 8-two (n-butoxy) benzo two thiophene-co-N, N '-two (n-decane base) isoindigo } product, productive rate 68%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=87.3kDa, M
w/ M
n=2.0.
Embodiment 5
The isoindigo base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,8-two (n-tetradecane oxygen base) benzo two thiophene-co-N, N '-di-n-hexyl isoindigo }, wherein, R
1Be n-tetradecane base, R
2Be the normal hexane base, n is 10, and its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
with 2, 6-two tin trimethyls-4, 8-two (n-tetradecane oxygen base) benzo two thiophene (282mg, 0.3mmol) and 6, 6 '-two bromo-N, N '-di-n-hexyl isoindigo (176mg, 0.3mmol) add and fill 15mLN, in the two-mouth bottle of the 50mL specification of dinethylformamide, be dissolved into solution, logical nitrogen and argon gas gas mixture, air-discharging is approximately after 20min, then with tetra-triphenylphosphine palladium (8mg, 0.006mmol) add in two-mouth bottle, fully lead to again nitrogen and argon gas gas mixture, continue air-discharging approximately after 10min, stir under 130 ℃, Stille coupling reaction 12h, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 4 after 50 ℃ of dry 24h under vacuum, 8-two (n-tetradecane oxygen base) benzo two thiophene-co-N, N '-di-n-hexyl isoindigo } product, productive rate is 76%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=11.8kDa, M
w/ M
n=2.3.
The isoindigo base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,8-two (n-octyloxy) benzo, two thiophene-co-N, N '-two dodecyl isoindigo }, wherein, R
1Be octane base, R
2Be dodecyl, n is 30, and its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
With 2,6-two tin trimethyls-4,8-two (n-octyloxy) benzo two thiophene (232mg, 0.3mmol), 6,6 '-two bromo-N, N '-two dodecyl isoindigo (227mg, 0.3mmol), three dibenzalacetone two palladium (13.75mg, 0.015mmol), tri-butyl phosphine (12.1mg, 0.06mmol) add in the flask that fills 12mL toluene, then logical nitrogen purge gas approximately after 30min, stir under 110 ℃, Stille coupling reaction 24h, stop polyreaction after cooling, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is under vacuum after 50 ℃ of dry 24h, be poly-{ 4,8-two (n-octyloxy) benzo two thiophene-co-N, N '-two dodecyl isoindigo } product, productive rate is 66%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=32.0kDa, M
w/ M
n=2.2.
Embodiment 7
The organic solar batteries of the present embodiment 7, its poly-{ 4,8-two (octyloxy) benzo, two thiophene-co-N, N '-dioctyl isoindigo } that adopts that embodiment 1 makes is the electron donor material of active coating.
See also Fig. 3, this organic solar batteries comprises glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14 and the negative electrode 15 that stacks gradually.Transparent anode 12 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/; Middle supplementary layer 13 adopts poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material (referred to as PEDOT:PSS); Active coating 14 comprises electron donor material and electron acceptor material, and electron donor material adopts poly-{ 4,8-two (octyloxy) benzo, two thiophene-co-N, the N '-dioctyl isoindigo } of embodiment 1 preparation, and electron acceptor material can be [6,6] phenyl-C
61-methyl-butyrate (referred to as PCBM); Negative electrode 15 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 150nm, 30nm, 130nm or 60nm.
Glass-base 11 can be used as bottom, during making, choose ito glass, and after ultrasonic cleaning, process supplementary layer 13 in the middle of applying with oxygen-Plasma on ito glass, in the middle of again the polymkeric substance of embodiment 1 preparation and electron acceptor material being coated on after by blend on supplementary layer 13, form active coating 14, and then by vacuum evaporation technology deposition cathode 15 on active coating 14, obtain above-mentioned solar cell device.This solar cell device also needs through heating 4h under 110 degrees centigrade of air tight conditions, drop to again room temperature, can effectively increase order and the regularity arranged between interior each group of molecule and molecule segment after device is annealed, improve transmission speed and the efficient of carrier mobility, and then improve photoelectric transformation efficiency.In the present embodiment, the thickness of negative electrode 15Al layer is respectively 150nm.
As shown in Figure 3, under illumination, light transmission glass-base 11 and ITO electrode 12, the conduction hole type electroluminescent material in active coating 14 absorbs luminous energy, and produces exciton, these excitons move to electron donor(ED)/acceptor material at the interface again, and with transfer transport to electron acceptor material, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to metallic cathode transmission and collected by negative electrode, the hole is along electron donor material to ito anode transmission and collected by anode freely, thereby forms photoelectric current and photovoltage, realizes opto-electronic conversion, during external load 16, can power to it.In this process, conduction hole type electroluminescent material can utilize luminous energy more fully because it has very wide spectral response range, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, is convenient to large batch of preparation.
Should be understood that, above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. isoindigo base co-polymer solar cell material with following structural formula (I):
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer.
2. the preparation method of an isoindigo base co-polymer solar cell material, is characterized in that, comprises the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
A：
B：
Wherein, in described compd A, R
1Be C
1～C
20Alkyl; In described compd B, R2 is C
1～C
20Alkyl;
S2, under oxygen-free environment, with described compd A and compd B according to the mol ratio add-on of 1: 1, add in the organic solvent that contains catalyzer, fully after the dissolving after carrying out Stille coupling reaction 12～96h under 70～130 ℃, obtain having following structural formula after the cooling stopped reaction described isoindigo base co-polymer solar cell material of (I):
In formula, n is 10～100 integer.
3. the preparation method of isoindigo base co-polymer solar cell material according to claim 2, is characterized in that, in described step S2, described catalyzer is organic palladium.
4. the preparation method of isoindigo base co-polymer solar cell material according to claim 3, is characterized in that, in described step S2, and, described organic palladium is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; The mol ratio of described organic palladium and described compd A is 1: 20～1: 100.
5. the preparation method of isoindigo base co-polymer solar cell material according to claim 2, is characterized in that, in described step S2, described catalyzer is the mixture of organic palladium and organophosphor ligand.
6. the preparation method of isoindigo base co-polymer solar cell material according to claim 5, is characterized in that, in described step S2, described organic palladium is three dibenzalacetone two palladiums, and described organophosphor ligand is tri-butyl phosphine; In described mixture, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8.
According to claim 3 to 6 arbitrary described isoindigo base co-polymer solar cell material the preparation method, it is characterized in that, in described step S2, described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
According to claim 3 to 6 arbitrary described isoindigo base co-polymer solar cell material the preparation method, it is characterized in that, in described step S2, described Stille coupling reaction temperature is 80～110 ℃; The described Stille coupling reaction time is 24～72h.
9. the application of isoindigo base co-polymer solar cell material claimed in claim 1 in the organic solar batteries active coating.
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| CN105367562A (en) * | 2015-11-20 | 2016-03-02 | 上海交通大学 | Di-bioxindol monomer and benzodithiophene double-tin copolymer preparation method, and purpose thereof |
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| CN105367561A (en) * | 2015-11-19 | 2016-03-02 | 上海交通大学 | Preparation and use of indole derivative and conjugated polymer thereof |
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| CN105418896A (en) * | 2015-12-02 | 2016-03-23 | 上海交通大学 | Preparation method of conjugated polymer of indole and thiophene compounds |
| CN105418897A (en) * | 2015-12-02 | 2016-03-23 | 上海交通大学 | Conjugated polymer of indole and thiophene compounds as well as preparation method and application thereof |
| CN105418897B (en) * | 2015-12-02 | 2017-12-15 | 上海交通大学 | Indoles and the conjugated polymer of fen class compound and its production and use |
| CN106046328A (en) * | 2016-01-26 | 2016-10-26 | 中国科学院化学研究所 | Silane-substituted two-dimensional conjugated polymer and preparation method thereof, and application of silane-substituted two-dimensional conjugated polymer to photovoltaic device |
| CN106046328B (en) * | 2016-01-26 | 2018-08-24 | 中国科学院化学研究所 | A kind of two-dimentional conjugated polymer of silane substituted and preparation method thereof and the application in photovoltaic device |
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