CN105585693B - Solar cell device - Google Patents
Solar cell device Download PDFInfo
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- CN105585693B CN105585693B CN201610115300.3A CN201610115300A CN105585693B CN 105585693 B CN105585693 B CN 105585693B CN 201610115300 A CN201610115300 A CN 201610115300A CN 105585693 B CN105585693 B CN 105585693B
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- Prior art keywords
- polymer
- compound
- unit containing
- solar cell
- bithiophene benzthiadiazole
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- 229920000642 polymer Polymers 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 55
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 claims abstract description 45
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims abstract description 45
- UUIQMZJEGPQKFD-UHFFFAOYSA-N Methyl butyrate Chemical compound CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 229940126062 Compound A Drugs 0.000 claims description 17
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 17
- 238000005859 coupling reaction Methods 0.000 claims description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- 229920000547 conjugated polymer Polymers 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 2
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 40
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 20
- 229910052763 palladium Inorganic materials 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 20
- 229930192474 thiophene Natural products 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
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- 238000001894 space-charge-limited current method Methods 0.000 description 10
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- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
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- 229910052786 argon Inorganic materials 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 7
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229920000144 PEDOT:PSS Polymers 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
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- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 5
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- UGYRYNXDEOFIQB-UHFFFAOYSA-N benzene thiophene Chemical compound S1C=CC=C1.C1=CC=CC=C1.C1=CC=CC=C1 UGYRYNXDEOFIQB-UHFFFAOYSA-N 0.000 description 4
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- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical class C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 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
- 238000005516 engineering process Methods 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 3
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 2
- 0 C[Sn](C)(C)c1cc(c(-c2ccc(*)[s]2)c2[s]c([Sn](C)(C)C)cc2c2-c3ccc(*)[s]3)c2[s]1 Chemical compound C[Sn](C)(C)c1cc(c(-c2ccc(*)[s]2)c2[s]c([Sn](C)(C)C)cc2c2-c3ccc(*)[s]3)c2[s]1 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- -1 benzal Chemical class 0.000 description 2
- 229940049706 benzodiazepine Drugs 0.000 description 2
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
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- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 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 description 2
- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical class COC1=CC=CC=C1P ORPNDFMZTDVBGA-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- WQCPSNAAWLHQAE-UHFFFAOYSA-N 2-bromo-4-methylthiophene Chemical class CC1=CSC(Br)=C1 WQCPSNAAWLHQAE-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical class CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- 241001614291 Anoplistes Species 0.000 description 1
- 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 description 1
- 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 description 1
- QBBOCSNLIYAOFH-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] QBBOCSNLIYAOFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
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- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical class [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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- C08G2261/18—Definition of the polymer structure conjugated
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- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
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- C08G2261/40—Polymerisation processes
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- C08G2261/50—Physical properties
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Abstract
A kind of solar cell device, including active layer, it is characterised in that the active layer includes electron donor material and electron acceptor material, and the electron acceptor material is [6,6] phenyl C61Methyl butyrate or [6,6] phenyl C71Methyl butyrate, the electron donor material have the polymer P of the unit containing bithiophene benzthiadiazole of following structural formula：Wherein, R C1~C20Alkyl, n be 10~100 integer.Bithiophene benzthiadiazole's based polyalcohol is Donor acceptor type conjugated polymer, it has higher hole mobility, high open-circuit voltage, preferable solubility property and filming performance, there is wider absorption region in the range of 300nm~800nm, and then solve solar cell device low efficiency problem.
Description
The application is the divisional application of following patent
Application number：2013100384967
The applying date：On 01 31st, 2013
Invention and created name：Polymer of the unit containing bithiophene benzthiadiazole and preparation method thereof and solar cell device
Part
【Technical field】
The present invention relates to photoelectric field, more particularly to a kind of preparation side of the polymer of unit containing bithiophene benzthiadiazole
Method.
【Background technology】
It is this to be referred to as " forth generation macromolecule " since Japanese Scientists Hideki Shirakawa in 1977 finds polyacetylene conduction
The conducting polymer of material has attracted numerous scientists to be studied with its photoelectric properties protruded.Conducting polymer is same to have phase
With or the inorganic material of similar use compared with, have density it is low, easy processing, synthesis range of choice it is wide the advantages that.Due to this kind of material
Expect structure conjugate property, enable it to transmit electric charge, stimulated luminescence, so as to or it is potentially possible in many electronics or photoelectron
It is applied on device, such as including polymer LED, photovoltaic cell, field-effect etc..Potential application prospect and
The field of being widely applied promotes scientist competitively to study this kind of conjugated material with photoelectric activity, including small point of conjugated structure
Son, and polyacetylene, polypyrrole, polythiophene, polyaniline, polyfluorene etc..
Researcher has been working hard seek to improve polymer LED, photovoltaic cell, field-effect
The method of energy, material is one of most important factor.So many research groups are directed to exploitation and have high-quantum efficiency always,
High color purity, the good light emitting polymer of long-time stability, and that visible-range absorption bands is wide, carrier mobility is high is poly-
Compound.These targets are realized, it is necessary to develop more new conjugated molecular materials and polymeric material, wherein, design synthesis
New conjugate unit just seems particularly significant.
【The content of the invention】
Based on this, it is necessary to provide a kind of polymerization of the higher unit containing bithiophene benzthiadiazole of energy conversion efficiency
Thing.
In addition, it there is a need to the preparation method that a kind of polymer of the unit containing bithiophene benzthiadiazole is provided.
In addition, it there is a need to the solar cell device that the polymer using the unit containing bithiophene benzthiadiazole is provided.
A kind of polymer of unit containing bithiophene benzthiadiazole, there is following structural formula：
P：
Wherein, R C1~C20Alkyl, n be 10~100 integer.
A kind of preparation method of the polymer of unit containing bithiophene benzthiadiazole, comprises the following steps：
Compound A and compound B that following structural formula represents are provided,
A is：B is：
Wherein, R C1~C20Alkyl；
In oxygen-free environment, compound A and compound B that mol ratio is 1: 1~1: 1.2 are added into containing catalyst
In organic solvent, Stille coupled reactions are carried out 6 hours~60 hours at 70 DEG C~130 DEG C, the catalyst be organic palladium or
For organic palladium and the mixture of organophosphor ligand, the polymerization for the unit containing bithiophene benzthiadiazole that following structural formula represents is obtained
Thing P：
Wherein, n is 10~100 integer.
The organic solvent is selected from least one of toluene, DMF and tetrahydrofuran.
The organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three dibenzalacetones two
Palladium, the organophosphorus ligand be tri-butyl phosphine, tri-o-tolyl phosphine or 2- dicyclohexyls phosphorus -2 ', 6 '-dimethoxy-biphenyl,
The mol ratio of the organic palladium and the organophosphorus ligand is 1: 4~1: 8.
The mol ratio of organic palladium and the compound A in the catalyst is 1: 20~1: 100.
The reaction temperature of the Stille coupled reactions is 90 DEG C~120 DEG C, and the reaction time is 12 hours~48 hours.
The step of also including being isolated and purified the polymer P of the unit containing bithiophene benzthiadiazole, the separation are pure
It is as follows to change step：Methanol precipitating and mistake are added in solution after carrying out from Stille coupled reactions to the compound A and compound B
Filter, the solid being filtrated to get is stripped with methanol and n-hexane successively, and the solid chloroform after extracting is received
Evaporation solvent obtains the polymer P of the unit containing bithiophene benzthiadiazole after purification after collection chloroformic solution.
The extracting is carried out using apparatus,Soxhlet's.
A kind of solar cell device, including active layer, the active layer include electron donor material and electron acceptor material
Material, the electron acceptor material is [6,6] phenyl-C61- methyl butyrate or [6,6]-phenyl-C71- methyl butyrate, the electricity
Sub- donor material has the polymer P of the unit containing bithiophene benzthiadiazole of following structural formula：
P：
Wherein, R C1~C20Alkyl, n be 10~100 integer.
The mol ratio of electron donor material and the electron acceptor material is 1: 2~1: 5.
The polymer of the above-mentioned unit containing bithiophene benzthiadiazole is donor-receiver type conjugated polymer, and it has higher
Hole mobility, high open-circuit voltage, preferable solubility property and filming performance, in the range of 300nm~800nm have compared with
Wide absorption region, it is a kind of polymer luminescent material of good performance, and then solves solar cell device low efficiency problem.
The preparation method of the polymer of the above-mentioned unit containing bithiophene benzthiadiazole, employs better simply synthetic route,
So as to reduce technological process, raw material are cheap and easy to get so that manufacturing cost reduces；It is molten and worth polymeric material constructions are novel
Solve functional, filming performance is excellent, is applicable to solar cell device.
【Brief description of the drawings】
Fig. 1 is the flow chart of the preparation method of the polymer of the unit containing bithiophene benzthiadiazole of an embodiment；
Fig. 2 is the structural representation of the solar cell device of an embodiment；
Fig. 3 is the uv-visible absorption spectra of the polymer of the unit containing bithiophene benzthiadiazole prepared by embodiment 1
Figure；
Fig. 4 is the thermogravimetic analysis (TGA) figure of the polymer of the unit containing bithiophene benzthiadiazole prepared by embodiment 1.
【Embodiment】
The content of patent for a better understanding of the present invention, this is further illustrated below by specific example and legend
The technology case of invention, specifically includes material preparation and prepared by device, but these embodiments are not intended to limit the present invention, wherein monomer
A is commercially obtained, and monomer B is commercially obtained.
The polymer of the unit containing bithiophene benzthiadiazole of one embodiment, there is following structural formula：
P：
Wherein, R C1~C20Alkyl, n be 10~100 integer.
The above-mentioned polymer for containing bithiophene benzthiadiazole's unit is donor-receiver type conjugated polymer, it have compared with
High hole mobility, high open-circuit voltage, preferable solubility property and filming performance, have in the range of 300nm~800nm
Wider absorption region, it is a kind of polymer luminescent material of good performance, is asked so as to solve solar cell device poor efficiency
Topic.
The preparation method of the polymer of the unit containing bithiophene benzthiadiazole of one embodiment, as shown in figure 1, including with
Lower step：
Step S1, compound A and compound B is provided.
Compound A structural formula is：Wherein, R C1~C20Alkyl.
Compound B structural formula is：
Step S2, the polymer P of the unit containing bithiophene benzthiadiazole is prepared.
In oxygen-free environment, compound A and compound B that mol ratio is 1: 1~1: 1.2 are added into containing catalyst
In organic solvent, Stille coupled reactions are carried out 6 hours~60 hours at 70 DEG C~130 DEG C, the catalyst be organic palladium or
The mixture of organic palladium and organophosphor ligand, obtain the polymer for the unit containing bithiophene benzthiadiazole that following structural formula represents
P：
Wherein, n is 10~100 integer.
In present embodiment, Stille coupled reactions are carried out under nitrogen atmosphere.
In present embodiment, organic solvent is selected from least one of toluene, DMF and tetrahydrofuran.
It is appreciated that other solvents can also be used in organic solution, as long as can dissolved compound A and compound B.
In present embodiment, organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three or two benzal
The palladium of benzylacetone two, organophosphorus ligand are tri-butyl phosphine, tri-o-tolyl phosphine or 2- dicyclohexyl phosphorus -2 ', and 6 '-dimethoxy joins
Benzene.The mol ratio of organic palladium and organophosphor ligand is 1: 4~1: 8 in the mixture of organic palladium and organophosphor ligand.Preferably, adopt
Catalyst is used as by the use of the mixture of the palladium of three dibenzalacetone two and tri-butyl phosphine.It is appreciated that organic palladium, organophosphor ligand
Cited species is not limited to, as long as can catalytic cpd A and compound B progress Stille coupled reactions.
In present embodiment, organic palladium and compound A mol ratio are 1: 20~1: 100 in catalyst.It is appreciated that have
The mol ratio of machine palladium and compound A is not limited to 1: 20~1: 100, adds into the organic solvent for adding compound A and compound B
Enter the catalyst of catalytic amount.
In present embodiment, the reaction temperatures of Stille coupled reactions is 70 DEG C~130 DEG C, the reaction time is 6 hours~
60 hours.Preferably, the reaction temperature of Stille coupled reactions is 90 DEG C~120 DEG C, and the reaction time is 12 hours~48 hours.
It is appreciated that the reaction temperature of Stille coupled reactions is not limited to 70 DEG C~130 DEG C, as long as can make compound A and compound B
React；Reaction time is also not necessarily limited to as 12 hours~48 hours, as long as compound A and compound B can be made as far as possible anti-
Should be complete.
Step S3, the polymer P of the unit containing bithiophene benzthiadiazole is isolated and purified.
Methanol precipitating is added in solution after carrying out from Stille coupled reactions to the compound A and compound B and is filtered,
The solid being filtrated to get is stripped with methanol and n-hexane successively, the solid chloroform after extracting is collected
Evaporation solvent obtains the polymer P of the unit containing bithiophene benzthiadiazole after purification after chloroformic solution.
In present embodiment, extract and carried out using apparatus,Soxhlet's.
In present embodiment, evaporation solvent after chloroformic solution will be collected and obtain after purification single containing bithiophene benzthiadiazole
50 DEG C under vacuo~70 DEG C of the polymer P of member, dry 24 hours~48 hours.
The preparation method of the polymer of the above-mentioned unit containing bithiophene benzthiadiazole, synthetic route is relatively simple, reduces
Manufacturing cost.
A kind of solar cell device in one embodiment, including active layer, the active layer include electron donor material
And electron acceptor material, the electron acceptor material are [6,6] phenyl-C61- methyl butyrate or [6,6]-phenyl-C71- butyric acid
Methyl esters, the electron donor material have the polymer P of the unit containing bithiophene benzthiadiazole of following structural formula：
Wherein, R C1~C20Alkyl, n be 10~100 integer.
In a preferred embodiment, the mol ratio of electron donor material and the electron acceptor material is 1: 2~1: 5.
It is specific embodiment below.
Embodiment 1
Present embodiment discloses the following poly- { thiophene of 2,6- diyl -4,8- bis- (5- normal octane bases thiophene) benzo two of structural formula
Fen-co-4,7- bis- (5- bases-thiophene -2- bases) diazosulfide } (polymer P 1 of the unit containing bithiophene benzthiadiazole)：
The preparation process of the polymer P 1 of the above-mentioned unit containing bithiophene benzthiadiazole is as follows：
Argon gas protection under, by 2,6- bis- tin trimethyl -4,8- bis- (5- normal octane bases thiophene) benzene thiophene (181mg,
0.2mmol), 4,7- bis- (5- bromothiophene -2- bases) diazosulfide (92mg, 0.2mmol) adds and fills 10ml toluene solvants
In flask, vacuumize deoxygenation and be filled with argon gas, then add bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol)；It will burn
Bottle is heated to 100 DEG C and carries out Stille coupled reactions 36h.Then, stop polymerisation after cooling, 50ml first is added dropwise into flask
Settled in alcohol；By extracting 24h with methanol and n-hexane successively after apparatus,Soxhlet's filtering.Then using chloroform as solvent
Extracting collects chloroformic solution and simultaneously is spin-dried for obtaining red powder to colourless, be pumped through under vavuum pump night obtain product it is poly- 2,6- diyls-
4,8- bis- (5- normal octane bases thiophene) benzene thiophene-co-4,7- bis- (5- bases-thiophene -2- bases) diazosulfides }, yield
78%.
The reaction equation of the polymer P 1 of above-mentioned preparation unit containing bithiophene benzthiadiazole is as follows：
Molecule measuring test result is：Molecular weight (GPC, THF, R.I)：Mn=36.8kDa, Mw/Mn=2.2.
It is the organic semiconducting materials P1 prepared in embodiment 1 UV-visible absorption spectrum referring to accompanying drawing 3, it is purple
Outside-visible absorption spectra measures on Jasco-570 uv analyzers.As seen from the figure：Inventive polymers in 300nm
There is larger wider absorption between~800nm, wherein maximum absorption band is located at 573nm, and wide absorption spectrum shows that P1 is a kind of
Photovoltaic material.
It is organic semiconducting materials P1 prepared by the present embodiment 1 thermogravimetic analysis (TGA) figure referring to accompanying drawing 4, thermogravimetric curve
(TGA) test is carried out on TA SDT 2960instruments, under nitrogen stream protection, programming rate 10K/min.By scheming
It can be seen that 5% thermal weight loss temperature (Td) it is 464 DEG C.
With ITO/PEDOT：The polymer P 1/Au of PSS/ the present embodiment 1 is device architecture, and the structure anode of the device uses oxygen
Change indium tin, Hole-injecting Buffer Layer for Improvement uses poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid (PEDOT：PSS), hole transmission layer
Using polymer P 1 manufactured in the present embodiment, negative electrode uses metallic aluminium, and is surveyed using space charge limited current (SCLC) model
Determine the hole mobility of polymer, the hole mobility for obtaining polymer is 5.7 × 10-5cm2/Vs。
Embodiment 2
Present embodiment discloses structural formula it is following it is poly- 2,6- diyl -4,8- bis- (5- methyls thiophene) benzene thiophenes -
Co-4,7- bis- (5- bases-thiophene -2- bases) diazosulfide } (polymer P 2 of the unit containing bithiophene benzthiadiazole)：
The preparation process of the polymer P 2 of the above-mentioned unit containing bithiophene benzthiadiazole is as follows：
Under nitrogen and argon gas mixing gas shielded, by 2,6- bis- tin trimethyl -4,8- bis- (5- methylthiophenes) benzene thiophene
(212mg, 0.3mmol), 4,7- bis- (5- bromothiophene -2- bases) diazosulfide (137mg, 0.3mmol) and 15mL tetrahydrofurans
Add in the two-mouth bottle of 50mL specifications, after being fully passed through the gaseous mixture air-discharging about 20min of nitrogen and argon gas after dissolving, then will
After tetra-triphenylphosphine palladium (4mg, 0.003mmol) is added thereto again the gaseous mixture air-discharging about 10min of fully logical nitrogen and argon gas,
Two-mouth bottle is added to 70 DEG C and carries out Stille coupled reactions 60h.Then, stop polymerisation after cooling, add into two-mouth bottle
Enter 40mL methanol precipitatings, by extracting 24h with methanol and n-hexane successively after apparatus,Soxhlet's filtering.Then using chloroform to be molten
Agent is extracted to colourless, is collected chloroformic solution and simultaneously is spin-dried for obtaining red solid, is produced under vacuo after 50 DEG C of dry 24h after collection
Poly- { 2,6- diyl -4,8- bis- (5- methyls thiophene) benzene thiophene-co-4,7- bis- (5- bases-thiophene -2- bases) the benzo thiophenes of thing
Diazole }.Yield is 82%.
The reaction equation of the polymer P 2 of above-mentioned preparation unit containing bithiophene benzthiadiazole is as follows：
Molecule measuring test result is：Molecular weight (GPC, THF, R.I)：Mn=27.1kDa, Mw/Mn=2.3.
The organic semiconducting materials P2 prepared in the present embodiment 2 UV-visible absorption spectrum, ultraviolet-ray visible absorbing
Spectrum measures on Jasco-570 uv analyzers.As seen from the figure：Inventive polymers between 300nm~800nm
There is larger wider absorption, wherein maximum absorption band is located at 572nm.
Organic semiconducting materials P2 prepared by the present embodiment 2 thermogravimetic analysis (TGA), thermogravimetric curve (TGA) are tested in TA
Carried out on SDT 2960instruments, under nitrogen stream protection, programming rate 10K/min.5% thermal weight loss temperature
(Td) it is 478 DEG C.
With ITO/PEDOT：The polymer P 2/Au of PSS/ the present embodiment 2 is device architecture, and the structure anode of the device uses oxygen
Change indium tin, Hole-injecting Buffer Layer for Improvement uses poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid (PEDOT：PSS), hole transmission layer
Using polymer P 2 manufactured in the present embodiment, negative electrode uses metallic aluminium, and is surveyed using space charge limited current (SCLC) model
Determine the hole mobility of polymer, the hole mobility for obtaining polymer is 6.2 × 10-5cm2/Vs。
Embodiment 3
Present embodiment discloses following poly- { 2,6- diyl -4,8- bis- (the 5- n-eicosane bases thiophene) benzos two of structural formula
Thiophene-co-4,7- bis- (5- bases-thiophene -2- bases) diazosulfide } (polymer P 3 of the unit containing bithiophene benzthiadiazole)：
The preparation process of the polymer P 3 of the above-mentioned unit containing bithiophene benzthiadiazole is as follows：
Nitrogen protection under, by 2,6- bis- tin trimethyl -4,8- bis- (5- n-eicosane bases thiophene) benzene thiophene (372mg,
0.3mmol), 4,7- bis- (the bromo- 4- methylthiophenes -2- bases of 5-) benzo [1,2,5] thiadiazoles (153mg, 0.33mmol), palladium
(3.5mg, 0.015mmol) and three (o-methoxyphenyl) phosphines (21mg, 0.06mmol) are added to the N for filling 12mL, N- diformazans
In the flask of base formamide, then toward after logical nitrogen purge gas about 20min in flask；Flask is heated to 130 DEG C of progress
Stille coupled reactions 12h.Then, stop polymerisation after cooling, 40mL methanol precipitatings are added into flask, are carried by Soxhlet
Take device filtering afterwards successively with methanol and n-hexane extracting 24h；Then using chloroform as solvent extraction to colourless, collection chloroformic solution
And be spin-dried for obtaining red powder, after collection under vacuo after 50 DEG C of dry 24h, the as poly- { (5- of 2,6- diyl -4,8- bis- of product
N-eicosane base thiophene) benzene thiophene-co-4,7- bis- (5- bases-thiophene -2- bases) diazosulfide }, yield 70%.
The reaction equation of the polymer P 3 of above-mentioned preparation unit containing bithiophene benzthiadiazole is as follows：
Molecule measuring test result is：Molecular weight (GPC, THF, R.I)：Mn=31.5kDa, Mw/Mn=2.2.
The organic semiconducting materials P3 prepared in the present embodiment 3 UV-visible absorption spectrum, ultraviolet-ray visible absorbing
Spectrum measures on Jasco-570 uv analyzers.As seen from the figure：Inventive polymers between 300nm~800nm
There is larger wider absorption, wherein maximum absorption band is located at 575nm.
Organic semiconducting materials P3 prepared by the present embodiment 3 thermogravimetic analysis (TGA), thermogravimetric curve (TGA) are tested in TA
Carried out on SDT 2960instruments, under nitrogen stream protection, programming rate 10K/min.5% thermal weight loss temperature
(Td) it is 449 DEG C.
With ITO/PEDOT：The polymer P 3/Au of PSS/ the present embodiment 3 is device architecture, and the structure anode of the device uses oxygen
Change indium tin, Hole-injecting Buffer Layer for Improvement uses poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid (PEDOT：PSS), hole transmission layer
Using polymer P 3 manufactured in the present embodiment, negative electrode uses metallic aluminium, and is surveyed using space charge limited current (SCLC) model
Determine the hole mobility of polymer, the hole mobility for obtaining polymer is 6.0 × 10-5cm2/Vs。
Embodiment 4
Present embodiment discloses the following poly- { thiophene of 2,6- diyl -4,8- bis- (5- normal butane bases thiophene) benzo two of structural formula
Fen-co-4,7- bis- (5- bases-thiophene -2- bases) diazosulfide } (polymer P 4 of the unit containing bithiophene benzthiadiazole)：
The preparation process of the polymer P 4 of the above-mentioned unit containing bithiophene benzthiadiazole is as follows：
Nitrogen protection under, by 2,6- bis- tin trimethyl -4,8- bis- (the positive two butane groups thiophene of 5-) benzene thiophene (238mg,
0.3mmol), 4,7- bis- (the bromo- 4- n-decanes base thiophene -2- bases of 5-) benzo [1,2,5] thiadiazoles (266mg, 0.36mmol), three
The palladium of two argon benzylacetone two (9mg, 0.009mmol) and 2- dicyclohexyls phosphine -2 ', 6 '-dimethoxy-biphenyl (29mg,
0.072mmol) it is added in the flask for the DMF for filling 12mL, then toward logical nitrogen purge gas in flask about
After 20min；Flask is heated to 90 DEG C and carries out Stille coupled reactions 24h.Then, polymerisation is stopped after cooling, to flask
Middle addition 40mL methanol precipitatings, by extracting 24h with methanol and n-hexane successively after apparatus,Soxhlet's filtering；Then with chloroform
It is solvent extraction to colourless, collects chloroformic solution and simultaneously be spin-dried for obtaining red powder, after collection under vacuo after 50 DEG C of dry 24h,
As poly- { 2,6- diyl -4,8- bis- (5- normal butane bases thiophene) (5- bases-thiophene -2- of benzene thiophene-co-4,7- bis- of product
Base) diazosulfide }, yield 81%.
The reaction equation of the polymer P 4 of above-mentioned preparation unit containing bithiophene benzthiadiazole is as follows：
Molecule measuring test result is：Molecular weight (GPC, THF, R.I)：Mn=74.6kDa, Mw/Mn=2.0.
The organic semiconducting materials P4 prepared in the present embodiment 4 UV-visible absorption spectrum, ultraviolet-ray visible absorbing
Spectrum measures on Jasco-570 uv analyzers.As seen from the figure：Inventive polymers between 300nm~800nm
There is larger wider absorption, wherein maximum absorption band is located at 570nm.
Organic semiconducting materials P4 prepared by the present embodiment 4 thermogravimetic analysis (TGA), thermogravimetric curve (TGA) are tested in TA
Carried out on SDT 2960instruments, under nitrogen stream protection, programming rate 10K/min.5% thermal weight loss temperature
(Td) it is 473 DEG C.
With ITO/PEDOT：The polymer P 4/Au of PSS/ the present embodiment 4 is device architecture, and the structure anode of the device uses oxygen
Change indium tin, Hole-injecting Buffer Layer for Improvement uses poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid (PEDOT：PSS), hole transmission layer
Using polymer P 4 manufactured in the present embodiment, negative electrode uses metallic aluminium, and is surveyed using space charge limited current (SCLC) model
Determine the hole mobility of polymer, the hole mobility for obtaining polymer is 6.0 × 10-5cm2/Vs。
Embodiment 5
Present embodiment discloses following poly- { 2,6- diyl -4,8- bis- (the 5- dodecyls thiophene) benzos two of structural formula
Thiophene-co-4,7- bis- (5- bases-thiophene -2- bases) diazosulfide } (polymer P 5 of the unit containing bithiophene benzthiadiazole)：
The preparation process of the polymer P 5 of the above-mentioned unit containing bithiophene benzthiadiazole is as follows：
Under nitrogen and argon gas mixing gas shielded, by 2,6- bis- tin trimethyl -4,8- bis- (5- dodecyls thiophene) benzo
Dithiophene (305mg, 0.3mmol), 4,7- bis- (the bromo- 4- n-hexanes base thiophene -2- bases of 5-) benzo [1,2,5] thiadiazoles
(188mg, 0.3mmol) and 15mL toluene are added in the two-mouth bottle of 50mL specifications, and the mixed of nitrogen and argon gas is fully passed through after dissolving
After closing gas air-discharging about 20min, then tetra-triphenylphosphine palladium (8mg, 0.006mmol) is added thereto, is passed through nitrogen and argon gas
Gaseous mixture air-discharging about 10min after, two-mouth bottle is added to 90 DEG C and carries out Stille coupled reactions 48h.Then, stop after cooling
Only polymerisation, 40mL methanol precipitatings are added into two-mouth bottle, by using methanol and just oneself after apparatus,Soxhlet's filtering successively
Alkane extracts 24h.Then be solvent extraction to colourless using chloroform, collect chloroformic solution and simultaneously be spin-dried for obtaining red solid, after collection
Poly- { 2,6- diyl -4,8- bis- (the 5- dodecyls thiophene) benzene thiophene-co- of product are obtained after the dry 24h of lower 50 DEG C of vacuum
4,7- bis- (5- bases-thiophene -2- bases) diazosulfides }.Yield is 75%.
The reaction equation of the polymer P 5 of above-mentioned preparation unit containing bithiophene benzthiadiazole is as follows：
Molecule measuring test result is：Molecular weight (GPC, THF, R.I)：Mn=52.0kDa, Mw/Mn=2.1.
The organic semiconducting materials P5 prepared in the present embodiment 5 UV-visible absorption spectrum, ultraviolet-ray visible absorbing
Spectrum measures on Jasco-570 uv analyzers.As seen from the figure：Inventive polymers between 300nm~800nm
There is larger wider absorption, wherein maximum absorption band is located at 556nm.
Organic semiconducting materials P5 prepared by the present embodiment 5 thermogravimetic analysis (TGA), thermogravimetric curve (TGA) are tested in TA
Carried out on SDT 2960instruments, under nitrogen stream protection, programming rate 10K/min.5% thermal weight loss temperature
(Td) it is 454 DEG C.
With ITO/PEDOT：The polymer P 5/Au of PSS/ the present embodiment 5 is device architecture, and the structure anode of the device uses oxygen
Change indium tin, Hole-injecting Buffer Layer for Improvement uses poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid (PEDOT：PSS), hole transmission layer
Using polymer P 5 manufactured in the present embodiment, negative electrode uses metallic aluminium, and is surveyed using space charge limited current (SCLC) model
Determine the hole mobility of polymer, the hole mobility for obtaining polymer is 7.1 × 10-5cm2/Vs。
Embodiment 6
Referring to Fig. 2, a kind of solar cell device 60 includes substrate 61, anode 62, cushion 63, active layer 64 and the moon
Pole 65.Anode 62, cushion 63, active layer 64 and negative electrode 65 are sequentially formed on 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 ITO (tin indium oxide), preferably
Ground, ITO are the tin indium oxides that square resistance is 10-20 Ω/.
Cushion 63 is formed at a side surface of the anode 62 away from substrate 61.The material of cushion 63 is poly- 3,4- Asias second two
Epoxide thiophene and polystyrene-sulfonic acid composite (PEDOT：PSS).
Active layer 64 is formed at a side surface of the cushion 63 away from anode 62.Active layer 64 include electron donor material and
The mol ratio of electron acceptor material, electron donor material and electron acceptor material is 1: 2, and wherein electron acceptor material is (6,6)
Phenyl-C61- methyl butyrate (PCBM), the polymerization for the unit containing bithiophene benzthiadiazole that electron donor material is prepared for the present invention
Thing P, in present embodiment, the P1 that is prepared in the embodiment one that electron donor material is.
Negative electrode 65 is formed at a side surface of the active layer 64 away from cushion 63.Negative electrode 65 can use aluminium electrode or double gold
Belong to layer electrode, such as Ca/Al or Ba/Al etc., its thickness are preferably 170nm, 150nm, 130nm or 100nm.Present embodiment
In, the material of negative electrode 65 is aluminium, thickness 170nm.
It is appreciated that cushion 63 can omit, now active layer 64 is formed directly into the surface of anode 62.
The manufacturing process of the solar cell device 60 is as follows：
Anode 62 is formed at behind a side surface of substrate 61 and carries out ultrasonic wave cleaning, and with after oxygen-Plasma processing,
The surface of anode 62 applies the PEDOT that last layer plays modification：PSS forms cushion 63.
One layer of active layer 64 is coated on cushion 64.The active layer 64 includes electron donor material and electron acceptor material
Material, wherein electron acceptor material is PCBM, the P1 prepared in the embodiment one that electron donor material is.
Negative electrode 65 is formed on the surface of active layer 64.In present embodiment, negative electrode 65 is the aluminium lamination formed by vacuum evaporation.It is cloudy
The thickness of pole 65 is 170nm.
In the present embodiment, the solar cell device 60 passes through 110 degrees Celsius 4 hours under confined conditions, then drop to room
Temperature, solar cell device can be effectively increased the order arranged between each group of intramolecular and molecule segment and rule after annealing
Whole degree, the transmission speed and efficiency of carrier mobility are improved, improve photoelectric transformation efficiency.
In AM1.5G100mW/cm2Under illumination, based on the body heterojunction that the copolymer p 1 in embodiment 1 is donor material
The energy conversion efficiency 3.6% of solar cell device 60.
For the solar cell device 60 in use, under light illumination, light passes through substrate 61 and anode 62, the biography in active layer 64
Lead cavity type electroluminescent material and absorb luminous energy, and produce exciton, these excitons move to the boundary of electron donor/acceptor material again
At face, and electronics is transferred to electron acceptor material, such as PCBM, realizes the separation of electric charge, so as to form free carrier, i.e.,
Free electronics and hole.These free electronics transmit along electron acceptor material to negative electrode 65 and collected by negative electrode, freely
Hole transmitted along electron donor material to anode 62 and collected by anode 62, so as to form photoelectric current and photovoltage, realize
Opto-electronic conversion, during external load, it can be powered.In the process, Conduction cavity type electroluminescent material is due to its tool
There is very wide spectral response range, can more fully utilize luminous energy, to obtain higher photoelectric transformation efficiency, increase solar energy
The electricity generation ability of battery device.And this organic material can also mitigate the quality of solar cell device, and pass through spin coating etc.
Technology can make, and be easy to large batch of preparation.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (2)
1. a kind of solar cell device, including active layer, it is characterised in that the active layer includes electron donor material and electricity
Sub- acceptor material, the electron acceptor material are [6,6] phenyl-C61- methyl butyrate or [6,6]-phenyl-C71- butyric acid first
Ester, the electron donor material have the polymer P of the unit containing bithiophene benzthiadiazole of following structural formula：
Wherein, R C1~C20Alkyl, n be 10~100 integer；
The polymer P of the unit containing bithiophene benzthiadiazole is prepared using following steps：
Compound A and compound B that following structural formula represents are provided,
A is：B is：
Wherein, R C1~C20Alkyl；
In oxygen-free environment, compound A and compound B that mol ratio is 1: 1~1: 1.2 are added into containing the organic of catalyst
In solvent, Stille coupled reactions are carried out 6 hours~60 hours at 70 DEG C~130 DEG C；Enter to the compound A and compound B
Methanol precipitating is added in solution after row Stille coupled reactions and is filtered, the solid being filtrated to get is used to methanol and just oneself successively
Alkane is stripped, and by the solid chloroform after extracting, is collected evaporation solvent after chloroformic solution and is obtained containing after purification
The polymer P of bithiophene benzthiadiazole's unit.
2. solar cell device according to claim 1, it is characterised in that the electron donor material and the electronics
The mol ratio of acceptor material is 1: 2~1: 5.
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| CN104086752A (en) * | 2014-05-16 | 2014-10-08 | 中国华能集团清洁能源技术研究院有限公司 | Benzodithiophene polymer, its preparation method, semiconductor composition containing it, and solar cell using it |
| CN107586379A (en) * | 2016-07-07 | 2018-01-16 | 南方科技大学 | Conjugated polymer containing chlorobenzothiadiazole, preparation method thereof and organic solar cell device |
| US10312444B2 (en) | 2016-10-06 | 2019-06-04 | International Business Machines Corporation | Organic semiconductors with dithienofuran core monomers |
| CN110536915B (en) * | 2017-04-25 | 2022-05-13 | 香港科技大学 | Vertical benzodithiophene-based donor-acceptor polymers for electronic and photonic applications |
| KR101997972B1 (en) * | 2017-08-16 | 2019-07-09 | 재단법인대구경북과학기술원 | Conductive polymers, the organic photovoltaic cell comprising the same, and the synthesis thereof |
| CN111278888A (en) * | 2018-01-10 | 2020-06-12 | 香港科技大学 | Chlorinated benzodithiophene-based polymers for photovoltaic applications |
| CN111205307B (en) * | 2020-02-27 | 2022-11-04 | 中国科学院宁波材料技术与工程研究所 | Thienobenzothiadiazoledione organic compound, and preparation method and application thereof |
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| CN102050940A (en) * | 2011-01-28 | 2011-05-11 | 华南理工大学 | Organic semiconductor material containing 6-R group- [1, 2, 5] thiazole [3, 4-g] benzotriazole and application thereof |
| CN102060982A (en) * | 2010-12-03 | 2011-05-18 | 华南理工大学 | Organic semiconductor material containing naphthalene [1, 2-c: 5, 6-c] di [1, 2, 5] thiadiazole and application thereof |
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| CN101875717B (en) * | 2010-07-20 | 2012-01-25 | 中南大学 | Copolymer of bithiophene diazosulfide and dibenzothiophene (BDT) and application thereof |
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| CN102060982A (en) * | 2010-12-03 | 2011-05-18 | 华南理工大学 | Organic semiconductor material containing naphthalene [1, 2-c: 5, 6-c] di [1, 2, 5] thiadiazole and application thereof |
| CN102050940A (en) * | 2011-01-28 | 2011-05-11 | 华南理工大学 | Organic semiconductor material containing 6-R group- [1, 2, 5] thiazole [3, 4-g] benzotriazole and application thereof |
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| CN105601889B (en) | 2018-01-09 |
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