CN104177600A - Polymer containing dithiazolebenzothiadiazole group, preparation method and organic solar cell device thereof - Google Patents
Polymer containing dithiazolebenzothiadiazole group, preparation method and organic solar cell device thereof Download PDFInfo
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- CN104177600A CN104177600A CN201310204378.9A CN201310204378A CN104177600A CN 104177600 A CN104177600 A CN 104177600A CN 201310204378 A CN201310204378 A CN 201310204378A CN 104177600 A CN104177600 A CN 104177600A
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- dithiazole
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 42
- UNTNRNUQVKDIPV-UHFFFAOYSA-N 3h-dithiazole Chemical compound N1SSC=C1 UNTNRNUQVKDIPV-UHFFFAOYSA-N 0.000 claims description 37
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 claims description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 238000006619 Stille reaction Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000638 solvent extraction Methods 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- DADZIMNFQANSAN-UHFFFAOYSA-N C(C1=CC=CC=C1)CC(C)=O.[Ar] Chemical compound C(C1=CC=CC=C1)CC(C)=O.[Ar] DADZIMNFQANSAN-UHFFFAOYSA-N 0.000 claims description 3
- YXPUNWKYPJPPFC-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P YXPUNWKYPJPPFC-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
- 125000005605 benzo group Chemical group 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 150000004867 thiadiazoles Chemical class 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- 125000000437 thiazol-2-yl group Chemical group [H]C1=C([H])N=C(*)S1 0.000 description 6
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical class C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 150000003233 pyrroles Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 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
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- -1 decyl thiazol-2-yl Chemical group 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical group CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical group CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P ORPNDFMZTDVBGA-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 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 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000011161 development 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
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 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
- 239000000178 monomer Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Photovoltaic Devices (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Belonging to the field of organic semiconductor materials, the invention discloses a polymer containing a dithiazolebenzothiadiazole group, a preparation method and an organic solar cell device thereof. The polymer has a structural formula shown as the specification, wherein R1 and R2 are both alkyl of C1-C20, and n is an integer of 10-94. In the dithiazolebenzothiadiazole group (DTBT) polymer provided by the invention, DTBT is an important electron acceptor unit and has the advantages of narrow band gap, high sunlight absorption coefficient and wide absorption range, etc., and dissolving performance can be adjusted by modification of alkyl flexible chain and other functional groups on thiazole. Dithiophene (DTP) has photophysical properties easy to modify, and the polymer of DTP shows excellent photovoltaic properties.
Description
Technical field
The present invention relates to organic semiconductor material field, relate in particular to a kind of polymkeric substance containing dithiazole diazosulfide base and preparation method thereof.The invention still further relates to use and contain the polymkeric substance of dithiazole diazosulfide base as the organic solar batteries device of active coating electron donor material.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.Organic semiconductor material with its raw material be easy to get, cheap, technique is simple, stability is strong, photovoltaic effect is good etc., and advantage receives 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 Photoinduced Electron transfer phenomena after, organic polymer solar cell becomes the focus of research gradually.The research of this respect has in recent years obtained development at full speed, but organic polymer solar cell is still much lower than the efficiency of conversion of inorganic solar cell.For organic polymer solar cell is on the actual application, the type material that exploitation has a higher-energy efficiency of conversion is still the top priority in this field.
Summary of the invention
The polymkeric substance containing dithiazole diazosulfide base that provides a kind of effciency of energy transfer higher is provided problem to be solved by this invention.
Technical scheme of the present invention is as follows:
Containing a polymkeric substance for dithiazole diazosulfide base, its structural formula is as follows:
In formula, R
1, R
2be C
1～C
20alkyl, integer between n is 10-94.
The present invention also provides the preparation method of the above-mentioned polymkeric substance containing dithiazole diazosulfide base, comprises the steps:
The compd A and the B that provide respectively following structural formula to represent,
A:
b:
wherein, R
1, R
2be C
1～C
20alkyl;
Under oxygen-free environment, the compd A that is 1:1～1.2 by mol ratio and B are added in the organic solvent that contains catalyzer and dissolve, under 70～130 ° of C, carry out Stille coupling reaction 6～60 hours subsequently, stop after coupling reaction, separating-purifying reaction solution, obtain following structural formula containing dithiazole diazosulfide based polyalcohol:
in formula, the integer that n is 10-94.
The preparation method of the described polymkeric substance containing dithiazole diazosulfide base, wherein, one or both in argon gas, nitrogen of oxygen-free environment form.
The preparation method of the described polymkeric substance containing dithiazole diazosulfide base, wherein, described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; Or
Described catalyzer is the mixture of organic palladium and organophosphorus ligand, and in mixture, the molar weight of organophosphorus ligand is 4～8 times of organic palladium molar weight; Described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl;
The mol ratio of described catalyzer and described compd A is 1:20～1:100.
The preparation method of the described polymkeric substance containing dithiazole diazosulfide base, wherein, described organic solvent is at least one in toluene, DMF, tetrahydrofuran (THF).
The preparation method of the described polymkeric substance containing dithiazole diazosulfide base, wherein, Stille coupling reaction temperature is 90～120 ° of C, the reaction times is 12～48 hours.
The preparation method of the described polymkeric substance containing dithiazole diazosulfide base, wherein, separating-purifying reaction solution comprises:
After coupling reaction, in reaction solution, add methyl alcohol precipitating, by apparatus,Soxhlet's, filter subsequently, using successively again methyl alcohol and normal hexane extracting, obtain organic phase, then take chloroform as solvent extraction organic phase is to colourless, collect chloroformic solution and be spin-dried for, after the dry 24h of the lower 50 ° of C of vacuum, obtain the described polymkeric substance containing dithiazole diazosulfide base.
The invention still further relates to a kind of organic solar batteries device, the electron donor material of its active coating adopts the polymkeric substance containing dithiazole diazosulfide base of following structural formula:
In formula, R
1, R
2be C
1～C
20alkyl, integer between n is 10-94.
In dithiazole diazosulfide base of the present invention (DTBT) polymkeric substance; important electron acceptor(EA) unit of DTBT; there is band gap narrower and sunlight is had to higher uptake factor and the wider advantages such as absorption region, on thiazole, can modify to regulate solubility property by functional groups such as alkyl flexible chains; Two Thienopyrroles (DTP) have the photophysical property of easy modification, its co-polymer has demonstrated good photovoltaic performance, and the polymer application that DTBT and DTP are prepared by the copolymerization of Stille coupling method can solve organic electroluminescence device low efficiency problem in solar cell.
The preparation method of above-mentioned dithiazole benzotriazole based polyalcohol, has adopted better simply synthetic route, thereby reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And worth polymeric material novel structure, solubility property is good, and film forming properties is good, and absorption region is wide, and effciency of energy transfer is improved.
Accompanying drawing explanation
Fig. 1 is the polymkeric substance ultraviolet-visible absorption spectroscopy figure containing dithiazole diazosulfide base of embodiment 1;
Fig. 2 is the structural representation of the organic solar batteries device of embodiment 6.
Embodiment
In order to understand better the content of patent of the present invention, below by concrete example and legend, further illustrate technology case of the present invention, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein the monomer of compd A, compd B is all bought and is obtained from the market.
Embodiment 1:
The polymkeric substance containing dithiazole diazosulfide base of the present embodiment, i.e. poly-{ 4-octane base-4H-bis-thieno-[3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(5-base-4-n-octyl thiazol-2-yl) benzo [1,2,5] thiadiazoles }, (wherein, R1 is octane base, and R2 is octane base, n=49), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under argon shield, by 4-octane base-2,6-bis-(tin trimethyl)-4H-bis-thieno-s [3,2-b:2', 3'-d] pyrroles (123mg, 0.2mmol), 4,7-bis-(the bromo-4-octane of 5-base thiazol-2-yl) benzo [1,2,5] thiadiazoles (137mg, 0.2mmol) adds in the flask that fills 10ml toluene solvant, vacuumizes deoxygenation and is filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol); Flask is heated to 100 ℃ and carries out Stille coupling reaction 36h.Subsequently, after cooling, stop polyreaction, to dripping in flask, in 50ml methyl alcohol, carry out sedimentation; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after the dry 24h of the lower 50 ° of C of vacuum, obtain product, gather { 4-octane base-4H-bis-thieno-s [3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(5-base-4-n-octyl thiazol-2-yl) benzo [1,2,5] thiadiazoles }, productive rate 86%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=47.2kDa, M
w/ M
n=2.2.
Fig. 1 is the polymkeric substance ultraviolet-visible absorption spectroscopy figure containing dithiazole diazosulfide base of embodiment 1.As shown in Figure 1, this polymkeric substance has large wider absorption between 300nm～700nm, and wherein maximum absorption band is positioned at 552nm left and right.
Embodiment 2:
The polymkeric substance containing dithiazole diazosulfide base of the present embodiment, i.e. poly-{ 4-methyl-4H-bis-thieno-[3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(5-base-4-NSC 62789 base thiazol-2-yl) benzo [1,2,5] thiadiazoles }, (wherein, R1 is methyl, and R2 is NSC 62789 base, n=94), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 4-methyl-2, 6-bis-(tin trimethyl)-4H-bis-thieno-s [3, 2-b:2', 3'-d] pyrroles (158mg, 0.3mmol), 4, 7-bis-(the bromo-4-NSC 62789 of 5-base thiazol-2-yl) benzo [1, 2, 5] thiadiazoles (305mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF), after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 70 ℃ and carry out Stille coupling reaction 60h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, obtain product, i.e. poly-{ 4-methyl-4H-bis-thieno-s [3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(5-base-4-NSC 62789 base thiazol-2-yl) benzo [1,2,5] thiadiazoles }.Productive rate is 83%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=98.5kDa, M
w/ M
n=2.0.
Embodiment 3:
The polymkeric substance containing dithiazole diazosulfide base of the present embodiment, i.e. poly-{ 4-NSC 62789 base-4H-bis-thieno-[3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(5-base-4-methylthiazol-2-yl) benzo [1,2,5] thiadiazoles }, (wherein, R1 is NSC 62789 base, and R2 is methyl, n=10), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by 4-NSC 62789 base-2,6-bis-(tin trimethyl)-4H-bis-thieno-s [3,2-b:2', 3'-d] pyrroles (236mg, 0.3mmol), 4,7-bis-(the bromo-4-methylthiazol-2-of 5-yl) benzo [1,2,5] thiadiazoles (153mg, 0.33mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join in the flask of the DMF that fills 12mL, in flask, lead to after the about 20min of nitrogen purge gas subsequently; Flask is heated to 130 ℃ and carries out Stille coupling reaction 6h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, obtain product, gather { 4-NSC 62789 base-4H-bis-thieno-s [3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(5-base-4-methylthiazol-2-yl) benzo [1,2,5] thiadiazoles }, productive rate is 78%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=13.4kDa, M
w/ M
n=2.5.
Embodiment 4:
The polymkeric substance containing dithiazole diazosulfide base of the present embodiment, i.e. poly-{ 4-normal-butyl-4H-bis-thieno-[3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(the positive decyl thiazol-2-yl of 5-base-4-) benzo [1,2,5] thiadiazoles }, (wherein, R1 is normal-butyl, and R2 is positive decyl, n=85), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by 4-normal-butyl-2,6-bis-(tin trimethyl)-4H-bis-thieno-s [3,2-b:2', 3'-d] pyrroles (168mg, 0.3mmol), 4,7-bis-(the bromo-4-n-decane of 5-base thiazol-2-yl) benzo [1,2,5] thiadiazoles (266mg, 0.36mmol), three or two argon benzyl acetone two palladium (9mg, 0.009mmol), with 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins the N that fills 12mL, in the flask of dinethylformamide, in flask, lead to after the about 20min of nitrogen purge gas subsequently; Flask is heated to 120 ℃ and carries out Stille coupling reaction 24h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, obtain product, gather { 4-normal-butyl-4H-bis-thieno-s [3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(the positive decyl thiazol-2-yl of 5-base-4-) benzo [1,2,5] thiadiazoles }, productive rate is 81%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=62.7kDa, M
w/ M
n=2.1.
Embodiment 5:
The polymkeric substance containing dithiazole diazosulfide base of the present embodiment, i.e. poly-{ 4-dodecyl-4H-bis-thieno-[3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(5-base-4-n-hexyl thiazol-2-yl) benzo [1,2,5] thiadiazoles }, (wherein, R1 is dodecyl, and R2 is n-hexyl, n=31), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 4-dodecyl-2, 6-bis-(tin trimethyl)-4H-bis-thieno-s [3, 2-b:2', 3'-d] pyrroles (202mg, 0.3mmol), 4, 7-bis-(the bromo-4-normal hexane of 5-base thiazol-2-yl) benzo [1, 2, 5] thiadiazoles (188mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene, after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 90 ℃ and carry out Stille coupling reaction 48h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, obtain product, i.e. poly-{ 4-dodecyl-4H-bis-thieno-s [3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(5-base-4-n-hexyl thiazol-2-yl) benzo [1,2,5] thiadiazoles }.Productive rate is 76%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=36.3kDa, M
w/ M
n=2.3.
Embodiment 6:
Refer to Fig. 2, a kind of organic solar batteries device 60 comprises substrate 61, anode 62, buffer layer 63, active coating 64 and negative electrode 65.Anode 62, buffer layer 63, active coating 64 and negative electrode 65 stack gradually a surface that is formed at substrate 61.
In the present embodiment, substrate 61 is glass.
Anode 62 is formed at a side surface of substrate 61.In the present embodiment, anode 62 is for being ITO(tin indium oxide), preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth.
Buffer layer 63 is formed at anode 62 away from a side surface of substrate 61.What the material of buffer layer 63 was poly-3,4-ethylenedioxy thiazole (PEDOT) and polystyrene-sulfonic acid matrix material (PSS) mixes, and is expressed as PEDOT:PSS.
Active coating 64 is formed at buffer layer 63 away from a side surface of anode 62.Active coating 64 comprises electron donor material and electron acceptor material, and the mol ratio of electron donor material and electron acceptor material is 1:2, and wherein electron acceptor material is (6,6) phenyl-C
61-methyl-butyrate (PCBM), electron donor material is the polymkeric substance containing dithiazole diazosulfide base prepared by the present invention.In present embodiment, the polymkeric substance containing dithiazole diazosulfide base of preparation in the embodiment 1 that electron donor material is, gather { 4-octane base-4H-bis-thieno-s [3,2-b:2', 3'-d] pyrroles-2,6-bis-bases-co-4,7-bis-(5-base-4-n-octyl thiazol-2-yl) benzo [1,2,5] thiadiazoles } (with P1, representing).
Negative electrode 65 is formed at active coating 64 away from a side surface of buffer layer 63.Negative electrode 65 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 150nm, 130nm or 100nm.In present embodiment, the material of negative electrode 65 is aluminium, and thickness is 170nm.
In another embodiment, buffer layer 63 can omit, and now active coating 64 is directly formed at anode 62 surfaces.
In the present embodiment 6, the manufacturing processed of organic solar batteries device 60 is as follows:
After anode 62 being formed to a side surface of substrate 61, carry out ultrasonic cleaning, and after processing with oxygen-Plasma, on anode 62 surfaces, be coated with the PEDOT:PSS that last layers play modification and form buffer layer 63.
On buffer layer 64, apply one deck active coating 64.This active coating 64 comprises electron donor material and electron acceptor material, and wherein electron acceptor material is PCBM, the P1 of preparation in the embodiment 1 that electron donor material is.
On active coating 64 surfaces, form negative electrode 65.In present embodiment, the aluminium lamination of negative electrode 65 for being formed by vacuum evaporation.The thickness of negative electrode 65 is 170nm.
In the present embodiment, this organic solar batteries device 60 was through lower 4 hours of 110 degrees Celsius of air tight conditions, drop to again room temperature, after solar cell device is annealed, can effectively increase order and the regularity between interior each group of molecule and molecule segment, arranged, improve transmission speed and the efficiency of carrier mobility, improve photoelectric transformation efficiency.
At AM1.5G100mW/cm
2under illumination, the effciency of energy transfer 2.8% of the body heterojunction organic solar batteries device 60 that the copolymer p 1 based in embodiment 1 is donor material.
When this organic solar batteries device 60 is used, under illumination, light transmission substrate 61 and anode 62, the conduction hole type electroluminescent material in active coating 64 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by 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 negative electrode 65, transmit and be collected by negative electrode, transmit and collected by anode 62 along electron donor material anode 62 in hole freely, thereby form photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In this process, conduction hole type electroluminescent material, because it has very wide spectral response range, can utilize luminous energy more fully, 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, be convenient to large batch of preparation.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. containing a polymkeric substance for dithiazole diazosulfide base, it is characterized in that, its structural formula is as follows:
In formula, R
1, R
2be C
1～C
20alkyl, integer between n is 10-94.
2. the polymkeric substance containing dithiazole diazosulfide base according to claim 2, is characterized in that, comprises a kind of in following polymkeric substance:
3. contain a preparation method for the polymkeric substance of dithiazole diazosulfide base, it is characterized in that, comprise the steps:
The compd A and the B that provide respectively following structural formula to represent,
A:
b:
wherein, R
1, R
2be C
1～C
20alkyl;
Under oxygen-free environment, the compd A that is 1:1～1.2 by mol ratio and B are added in the organic solvent that contains catalyzer and dissolve, under 70～130 ° of C, carry out Stille coupling reaction 6～60 hours subsequently, stop after coupling reaction, separating-purifying reaction solution, obtain following structural formula containing the polymkeric substance of dithiazole diazosulfide base:
in formula, the integer that n is 10-94.
4. the preparation method of the polymkeric substance containing dithiazole diazosulfide base according to claim 3, is characterized in that, described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; The mol ratio of described catalyzer and described compd A is 1:20～1:100.
5. the preparation method of the polymkeric substance containing dithiazole diazosulfide base according to claim 3, it is characterized in that, described catalyzer is the mixture of organic palladium and organophosphorus ligand, and in mixture, the molar weight of organophosphorus ligand is 4～8 times of organic palladium molar weight; The mol ratio of described catalyzer and described compd A is 1:20～1:100.
6. the preparation method of the polymkeric substance containing dithiazole diazosulfide base according to claim 5, is characterized in that, described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl.
7. the preparation method of the polymkeric substance containing dithiazole diazosulfide base according to claim 3, is characterized in that, described organic solvent is at least one in toluene, DMF, tetrahydrofuran (THF).
8. the preparation method of the polymkeric substance containing dithiazole diazosulfide base according to claim 3, is characterized in that, Stille coupling reaction temperature is 90～120 ° of C, and the reaction times is 12～48 hours.
9. the preparation method of the polymkeric substance containing dithiazole diazosulfide base according to claim 3, is characterized in that, separating-purifying reaction solution comprises:
After coupling reaction, in reaction solution, add methyl alcohol precipitating, by apparatus,Soxhlet's, filter subsequently, using successively again methyl alcohol and normal hexane extracting, obtain organic phase, then take chloroform as solvent extraction organic phase is to colourless, collect chloroformic solution and be spin-dried for, after the dry 24h of the lower 50 ° of C of vacuum, obtain the described polymkeric substance containing dithiazole diazosulfide base.
10. an organic solar batteries device, is characterized in that, the electron donor material of its active coating adopts the polymkeric substance containing dithiazole diazosulfide base of following structural formula:
In formula, R
1, R
2be C
1～C
20alkyl, integer between n is 10-94.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111732598A (en) * | 2020-07-09 | 2020-10-02 | 吉首大学 | A class of compounds containing dithiazolothiadiazole bi-heterocycle and preparation method thereof |
| CN114163618A (en) * | 2022-01-27 | 2022-03-11 | 香港中文大学（深圳） | Narrow-bandgap polymer based on benzodithiadiazole or thiadiazole quinoxaline, and preparation method and application thereof |
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| WO2011085004A2 (en) * | 2010-01-05 | 2011-07-14 | Konarka Technologies, Inc. | Photovoltaic cell with benzodithiophene-containing polymer |
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2013
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| WO2011085004A2 (en) * | 2010-01-05 | 2011-07-14 | Konarka Technologies, Inc. | Photovoltaic cell with benzodithiophene-containing polymer |
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| SARADA P. MISHRA ET AL: "Dithieno[3,2-b:2′,3′-d]pyrrole-Alkylthiophene-Benzo[c][1,2,5]thiadiazole-Based Highly Stable and Low Band Gap Polymers for Polymer Light-Emitting Diodes", 《JOURNAL OF POLYMER SCIENCE:PART A:POLYMER CHEMSTRY》, vol. 47, 31 December 2009 (2009-12-31), pages 6514 - 6525 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732598A (en) * | 2020-07-09 | 2020-10-02 | 吉首大学 | A class of compounds containing dithiazolothiadiazole bi-heterocycle and preparation method thereof |
| CN114163618A (en) * | 2022-01-27 | 2022-03-11 | 香港中文大学（深圳） | Narrow-bandgap polymer based on benzodithiadiazole or thiadiazole quinoxaline, and preparation method and application thereof |
| CN114163618B (en) * | 2022-01-27 | 2023-12-22 | 香港中文大学（深圳） | Narrow bandgap polymers based on benzobisthiadiazole or thiadiazolequinoxaline and their preparation methods and applications |
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