CN107629047B - Asymmetric organic small-molecule photovoltaic material based on benzothiadiazole unit and preparation method and application thereof - Google Patents
Asymmetric organic small-molecule photovoltaic material based on benzothiadiazole unit and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 53
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical group C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000003384 small molecules Chemical class 0.000 title claims description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 84
- 239000005964 Acibenzolar-S-methyl Substances 0.000 claims abstract description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 32
- 229940126062 Compound A Drugs 0.000 claims description 20
- 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 20
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
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- 239000012043 crude product Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
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- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- -1 2-cyano-styryl Chemical group 0.000 abstract description 32
- 238000010521 absorption reaction Methods 0.000 abstract description 26
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 9
- 125000005504 styryl group Chemical group 0.000 abstract description 7
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 229920002994 synthetic fiber Polymers 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- 230000009102 absorption Effects 0.000 description 24
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- 238000006555 catalytic reaction Methods 0.000 description 10
- 238000011160 research Methods 0.000 description 10
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- 238000002484 cyclic voltammetry Methods 0.000 description 8
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- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 7
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- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 5
- 238000003461 Miyaura Borylation reaction Methods 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
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- 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 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000021615 conjugation Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 4
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- 239000012074 organic phase Substances 0.000 description 4
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- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 3
- OWWVTWHBNAWUJO-UHFFFAOYSA-N 4-iodo-n,n-diphenylaniline Chemical compound C1=CC(I)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 OWWVTWHBNAWUJO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 3
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- 239000010409 thin film Substances 0.000 description 3
- KVOBAYUCRZIKLM-UHFFFAOYSA-N 1,2,3-benzothiadiazole N,N-diphenylaniline Chemical compound C1=CC=C2SN=NC2=C1.C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 KVOBAYUCRZIKLM-UHFFFAOYSA-N 0.000 description 2
- NXMBFPCGRZCQNV-UHFFFAOYSA-N 1,2-dinitro-4,5-dioctoxybenzene Chemical compound CCCCCCCCOC1=CC([N+]([O-])=O)=C([N+]([O-])=O)C=C1OCCCCCCCC NXMBFPCGRZCQNV-UHFFFAOYSA-N 0.000 description 2
- FNLUIKNPCILERZ-UHFFFAOYSA-N 1,2-dioctoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1OCCCCCCCC FNLUIKNPCILERZ-UHFFFAOYSA-N 0.000 description 2
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 2
- VGCVJZVDAAWTFC-UHFFFAOYSA-N 4,7-dibromo-5,6-dioctoxy-2,1,3-benzothiadiazole Chemical compound BrC1=C(OCCCCCCCC)C(OCCCCCCCC)=C(Br)C2=NSN=C21 VGCVJZVDAAWTFC-UHFFFAOYSA-N 0.000 description 2
- UESSERYYFWCTBU-UHFFFAOYSA-N 4-(n-phenylanilino)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UESSERYYFWCTBU-UHFFFAOYSA-N 0.000 description 2
- ZYDLDMVHUXTEEE-UHFFFAOYSA-N 4-[2-(4-bromophenyl)ethenyl]-n,n-diphenylaniline Chemical compound C1=CC(Br)=CC=C1C=CC1=CC=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 ZYDLDMVHUXTEEE-UHFFFAOYSA-N 0.000 description 2
- SQTLUXJWUCHKMT-UHFFFAOYSA-N 4-bromo-n,n-diphenylaniline Chemical compound C1=CC(Br)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 SQTLUXJWUCHKMT-UHFFFAOYSA-N 0.000 description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
- QDYFCLVSLUZDHB-UHFFFAOYSA-N 4-ethynyl-n,n-diphenylaniline Chemical compound C1=CC(C#C)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 QDYFCLVSLUZDHB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZQUPUKAVWZAXJS-UHFFFAOYSA-N C1=CC(Br)=CC=C1C#CC1=CC=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 Chemical compound C1=CC(Br)=CC=C1C#CC1=CC=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 ZQUPUKAVWZAXJS-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical group [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 2
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- VCTOBYVXMXHLOD-UHFFFAOYSA-N n,n-diphenyl-4-(2-trimethylsilylethynyl)aniline Chemical compound C1=CC(C#C[Si](C)(C)C)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 VCTOBYVXMXHLOD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- QJPQVXSHYBGQGM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 description 2
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- 125000004434 sulfur atom Chemical group 0.000 description 2
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- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- MFHFWRBXPQDZSA-UHFFFAOYSA-N 2-(4-bromophenyl)acetonitrile Chemical compound BrC1=CC=C(CC#N)C=C1 MFHFWRBXPQDZSA-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- GNYCNFWCQGDJRG-UHFFFAOYSA-N 5,6-dioctoxy-2,1,3-benzothiadiazole Chemical compound C1=C(OCCCCCCCC)C(OCCCCCCCC)=CC2=NSN=C21 GNYCNFWCQGDJRG-UHFFFAOYSA-N 0.000 description 1
- OFASHBNFIJSKDJ-UHFFFAOYSA-N 5,6-dioctoxy-4,7-dithiophen-2-yl-2,1,3-benzothiadiazole Chemical compound C12=NSN=C2C(C=2SC=CC=2)=C(OCCCCCCCC)C(OCCCCCCCC)=C1C1=CC=CS1 OFASHBNFIJSKDJ-UHFFFAOYSA-N 0.000 description 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
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- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses a benzothiadiazole asymmetric organic micromolecule photovoltaic material as well as a preparation method and application thereof, belonging to the field of photoelectric materials. The D-pi-A-A 'type asymmetric molecule takes benzothiadiazole as an A unit, triphenylamine as a D unit, phenyl, styryl, 2-cyano-styryl and phenylethynyl as pi connecting bonds respectively, and dicyanovinyl as an A' end group. In addition, different pi bridges cooperate with the A' end groups to enhance ICT action and reduce the HOMO level of the molecule. The 2-cyano-styryl linkage widens the absorption range of the molecule; the introduction of phenyl or 2-cyano-styryl reduces the HOMO energy level of the molecule, so that VocOver 1.0V. The PCE of the synthetic material can reach 2.43 percent at most, and the compound has clear structure, good solubility and film forming property and has the potential of being used as a high-efficiency asymmetric organic small molecular donor photovoltaic material.
Description
Technical Field
The invention relates to a benzothiadiazole asymmetric organic micromolecule photovoltaic material, a preparation method thereof and a solar cell device using the benzothiadiazole organic micromolecule as a donor material, belonging to the field of organic photoelectric materials.
Background
Compared with polymers, organic small molecules have the advantages of easy modification of structure, simple purification and preparation, low manufacturing cost of photovoltaic devices and the like, and become main research contents of organic photovoltaics. At present, the Photoelectric Conversion Efficiency (PCE) of the symmetrical organic small molecule donor material in the solution process is up to 11.3 percent, and is very close to the PCE of the current polymer donor material, which shows that the research of the organic small molecule donor material has theoretical and practical application values. Compared with polymer donor materials, the types of small organic molecule donor materials are still few, the PCE is generally low, and especially the types of asymmetric small organic molecule donor materials are fewer. Therefore, in order to broaden the research scope of organic small molecule donor materials, the invention aims to design and synthesize a novel asymmetric organic small molecule donor material.
Most studies have shown that electron-donating-electron-withdrawing units (D-A) are present) The material with the conjugated structure can effectively realize the charge transmission effect (namely ICT effect) in molecules, thereby improving the short-circuit current density (J) of the materialsc). Therefore, the structure with the D-A conjugation is important for improving the performance of the organic small molecule photovoltaic material. Compared with molecules with symmetrical structures, the asymmetrical molecules have more obvious electron pushing-pulling effect. A large number of researches show that the benzothiadiazole unit is widely applied to the fields of organic photovoltaics, organic field effect transistors and the like due to the advantages of good planarity, strong electron absorption, easy structure modification and the like. By means of alkoxylation on the benzothiadiazole unit, the solubility of the compound can be improved, and weak non-covalent bond (O- - -S) exists between an oxygen atom on the alkoxy and a sulfur atom on a thiophene ring, so that the overall planarity of the molecule is improved to a certain extent. Meanwhile, Dicyanovinyl (DCV) is a strong electron-deficient group, can enhance the ICT effect of molecules to a certain extent, and is common in the structure of dye-sensitized materials. At present, the PCE of symmetric organic small molecule donor materials based on diazosulfide units reaches 6.5%. However, the PCE based on the asymmetric material of the cell is also only 3.4% compared to the symmetric material. In addition, it is worth mentioning that V of such materialsocAlso below 1.0V. This indicates that there is still less research on benzothiadiazole asymmetric organic small molecule photovoltaic materials. Meanwhile, the adjustment of the energy level of the structure by pi conjugate bonds with different electron withdrawing properties is lack of systematic research, and the PCE and V of the corresponding photovoltaic deviceocAnd is also generally lower.
Disclosure of Invention
In order to solve the problems, the invention aims to enrich the research range of the benzothiadiazole asymmetric organic micromolecule photovoltaic material, and improves V by introducing pi-bridge bonds with different electron-withdrawing capabilities into a molecular structure and reducing the molecular HOMO energy level and the band gapocAnd JscAnd a certain theoretical basis is laid for the research of developing novel and efficient benzothiadiazole asymmetric small molecular donor materials.
The invention provides a benzothiadiazole asymmetric organic micromolecule, which has the following structure:
wherein X is a pi bond, each is
R is C1-C8 alkyl. R in the structural formula is the same.
The invention also aims to provide a synthesis method of the benzothiadiazole asymmetric organic small molecule photovoltaic material, which comprises the following steps:
under the protection of nitrogen, the compound A and the compound D are put into a Suzuki coupling reaction system catalyzed by palladium according to the equivalent ratio of 1:2.2, cross coupling reaction is carried out at 110 ℃, the reaction time is 48 hours, and the crude product is separated and purified by column chromatography to obtain the organic micromolecule Q.
Compounds D and a are represented by the following structures:
compound D is:
compound a is:
r is C1-C8 alkyl.
(1) When X represents phenyl, adding the compound A and the compound D into a Suzuki coupling reaction system which takes potassium carbonate as alkali and tetrakis (triphenylphosphine) palladium as a catalyst according to the equivalent ratio of 1: 2.2. The equivalent ratio of potassium carbonate to compound A was 1:40, and the equivalent ratio of catalyst to compound A was 1: 10. The reaction mixture was refluxed at 110 ℃ for 48 hours. The crude product was subjected to column chromatography to afford red compound Q1, having the formula:
(2) when X represents styryl, adding the compound A and the compound D into a Suzuki coupling reaction system which takes potassium carbonate as alkali and tetrakis (triphenylphosphine) palladium as a catalyst according to the equivalent ratio of 1: 2.2. The equivalent ratio of potassium carbonate to compound A was 1:40, and the equivalent ratio of catalyst to compound A was 1: 10. The reaction mixture was refluxed at 110 ℃ for 48 hours. The crude product was subjected to column chromatography to afford red compound Q2, having the formula:
(3) when X represents 2-cyano-styryl, adding the compound A and the compound D into a Suzuki coupling reaction system which takes potassium carbonate as alkali and tetrakis (triphenylphosphine) palladium as a catalyst according to the equivalent ratio of 1: 2.2. The equivalent ratio of potassium carbonate to compound A was 1:40, and the equivalent ratio of catalyst to compound A was 1: 10. The reaction mixture was refluxed at 110 ℃ for 48 hours. The crude product was subjected to column chromatography to afford red compound Q3, having the formula:
(4) when X represents phenylethynyl, adding the compound A and the compound D into a Suzuki coupling reaction system which takes potassium carbonate as alkali and tetrakis (triphenylphosphine) palladium as a catalyst according to the equivalent ratio of 1: 2.2. The equivalent ratio of potassium carbonate to compound A was 1:40, and the equivalent ratio of catalyst to compound A was 1: 10. The reaction mixture was refluxed at 110 ℃ for 48 hours. The crude product was subjected to column chromatography to afford red compound Q4, having the formula:
the benzothiadiazole asymmetric molecule can be used as a donor material of an organic micromolecule solar photovoltaic device, and the donor material and a receptor material [6,6 ]]-phenyl-C61-butyric acid methyl ester (PC)61BM) blendingThe compound is used as an optical active layer and is applied to the research of a solution process bulk heterojunction solar cell.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the asymmetric organic micromolecules containing different pi-bridge bonds and based on the diazosulfide unit are systematically synthesized for the first time, and can be used as donor materials to be applied to the field of organic micromolecule solar cells in the solution process.
(2) The introduction of an alkoxy chain on a benzothiadiazole unit is used for improving the solubility of the material, and meanwhile, a thiophene group is used for replacing a benzothiadiazole nucleus, and the planarity of a molecular skeleton is improved to a certain extent through the weak non-covalent bond action between a sulfur atom on thiophene and an oxygen atom (S- - -O) on the benzothiadiazole nucleus. In addition, four pi bridges of phenyl, styryl, 2-cyano-styryl and phenylethynyl are introduced to increase the conjugation degree of molecules and improve the charge transport effect (i.e. ICT effect) in the molecules.
(3) The invention introduces four pi-bridge bonds into the asymmetric organic micromolecule donor material for the first time, and all the materials obtain high V of more than 0.9Voc. Wherein the bridge materials Q1 and Q3 containing phenyl and 2-cyano-styryl respectively obtain V of 1.01V and 1.03VocThis also indicates that these two pi bridges are superior to styryl and phenylethynyl in lowering the HOMO level of the material.
(4) Under the condition of not optimizing any device, the primary photovoltaic test result shows that the optimal result of the photovoltaic device taking the benzothiadiazole target molecule as a donor in the invention is as follows: j. the design is a squarescIs 7.96mAcm-2，Voc1.03V, a Fill Factor (FF) of 0.30 and a PCE of 2.43%. The compound has the potential of being used as a high-efficiency organic small-molecule photovoltaic material, and the research idea is widened for developing a novel and high-efficiency asymmetric photovoltaic material.
Drawings
FIG. 1 is a normalized UV-Vis spectral absorption plot of Q1 in chloroform solution and in film-forming state in example 1;
FIG. 2 isQ1 in example 1 was determined at 0.1M tetrabutylammonium tetrafluoroborate/dichloromethane (Bu)4NBF4/CH2Cl2) Cyclic voltammograms in solution;
FIG. 3 shows Q1 and PC in example 161BM at a mass mixing ratio of 1: 3(w/w) and a total concentration of 12mgmL-1Current-voltage curves of the devices;
FIG. 4 is a normalized UV-Vis spectral absorption plot of Q2 in chloroform solution and in film-forming state for example 2;
FIG. 5 is a 0.1M tetrabutylammonium tetrafluoroborate/dichloromethane (Bu) solution of Q2 from example 24NBF4/CH2Cl2) Cyclic voltammograms in solution;
FIG. 6 shows Q2 and PC in example 261BM at a mass mixing ratio of 1: 3(w/w) and a total concentration of 12mgmL-1Current-voltage curves of the devices;
FIG. 7 is a normalized UV-Vis spectral absorption plot of Q3 in chloroform solution and in film-forming state for example 3;
FIG. 8 is a 0.1M tetrabutylammonium tetrafluoroborate/dichloromethane (Bu) solution of Q3 in example 34NBF4/CH2Cl2) Cyclic voltammograms in solution;
FIG. 9 shows Q3 and PC in example 361BM at a mass mixing ratio of 1: 3(w/w) and a total concentration of 12mgmL-1Current-voltage curves of the devices;
FIG. 10 is a normalized UV-Vis spectral absorption plot of Q4 in chloroform solution and in film-forming state for example 4;
FIG. 11 is a 0.1M tetrabutylammonium tetrafluoroborate/dichloromethane (Bu) solution of Q4 in example 44NBF4/CH2Cl2) Cyclic voltammograms in solution;
FIG. 12 shows Q4 and PC in example 461BM at a mass mixing ratio of 1: 3(w/w) and a total concentration of 12mgmL-1Current-voltage curve of the device.
Detailed Description
The present invention will be further described with reference to the following examples.
Part of the synthesis of compound a was carried out according to the reported literature (chem. commun.,2012,48, 10627-10629; chem. commun.,2013,49,9938-9940) with the following steps: using catechol as an initial raw material, and carrying out alkylation reaction on the catechol and n-bromooctane under the condition of potassium carbonate and acetone to generate 1, 2-di (n-octyloxy) benzene; 1, 2-di (n-octyloxy) benzene is subjected to nitration reaction in concentrated nitric acid and acetic acid to generate 1, 2-dinitro-4, 5-di (n-octyloxy) benzene; 1, 2-dinitro-4, 5-di (n-octyloxy) benzene and stannous chloride hydrate are subjected to reduction reaction in ethanol and concentrated hydrochloric acid to generate 1, 2-dinitro-4, 5-di (n-octyloxy) hydrochloride; 1, 2-binitro-4, 5-di (n-octyloxy) benzene hydrochloride and thionyl chloride are subjected to cyclization reaction in a triethylamine and dichloromethane solution to generate 5, 6-di (n-octyloxy) - [2,1,3] -benzothiadiazole; brominating 5,6- (n-octyloxy) - [2,1,3] -benzothiadiazole with liquid bromine and 40% hydrobromic acid at 120 ℃ to generate 4, 7-dibromo-5, 6-di (n-octyloxy) - [2,1,3] -benzothiadiazole; 4, 7-dibromo-5, 6-di (n-octyloxy) - [2,1,3] -benzothiadiazole and tributyl (thiophene-2-yl) tin are refluxed under the conditions of catalysis of bis (triphenylphosphine) palladium dichloride and 70 ℃ to generate Stille coupling reaction to generate 5, 6-di (n-octyloxy) -4, 7-di (thiophene-2-yl) - [2,1,3] -benzothiadiazole; under the condition of room temperature and light shielding, 5, 6-di (N-octyloxy) -4, 7-di (thiophene-2-yl) - [2,1,3] -benzothiadiazole and N-bromosuccinimide (NBS) are subjected to monobromo reaction on a thiophene ring in a chloroform solution to generate 4- (5-bromothiophene-2-yl) -5, 6-di (N-octyloxy) -7- (thiophene-2-yl) - [2,1,3] -benzothiadiazole; 4- (5-bromothien-2-yl) -5, 6-bis (N-octyloxy) -7- (thien-2-yl) - [2,1,3] -benzothiadiazole was subjected to Vilsmeil formylation in N, N-Dimethylformamide (DMF) and phosphorus oxychloride solution to produce a red compound A.
The specific synthetic route of the above reaction is as follows:
wherein R is C1-C8 alkyl;
the synthesis of compounds D1-D4 was carried out according to the procedure reported in the literature (J. Mater. chem.C,2014,2, 4019-4026; org. Electron, 2014,15,1138-1148) and the procedure was as follows:
(1) when X represents phenyl, triphenylamine is taken as an initial raw material to perform bromination reaction with NBS to generate 4-bromotriphenylamine; 4-bromotriphenylamine and pinacol ester diboronate are subjected to Miyaura borylation reaction under the catalysis of bis (triphenylphosphine) palladium dichloride to generate N, N-diphenyl-4- (4,4,5, 5-tetramethyl- [2,1,3] dioxoborane-2-yl) aniline; carrying out Suzuki cross-coupling reaction on N, N-diphenyl-4- (4,4,5, 5-tetramethyl- [2,1,3] dioxaborolan-2-yl) aniline and 4-bromoiodobenzene under the catalysis of tetrakis (triphenylphosphine) palladium to generate N, N-diphenyl-4' -bromo-4-benzidine; the compound D1 is produced by the Miyaura borylation reaction of N, N-diphenyl-4' -bromo-4-benzidine and pinacol ester diboron under the catalysis of bis (triphenylphosphine) palladium dichloride.
(2) When X represents styryl, triphenylamine and N-iodosuccinimide (NIS) are subjected to iodination reaction to generate 4-iodotriphenylamine; 4-iodotriphenylamine and 4-bromostyrene are subjected to Heck reaction under the catalysis of palladium acetate to generate 4- (2- (4-bromophenyl) vinyl) -N, N-diphenylaniline; 4- (2- (4-bromophenyl) vinyl) -N, N-diphenylaniline and pinacol ester diboron are subjected to Miyaura Borylation reaction under the catalysis of bis (triphenylphosphine) palladium dichloride to generate a compound D2.
(3) When X represents 2-cyano-styryl, triphenylamine undergoes Vilsmeier formylation in DMF and phosphorus oxychloride solution to generate 4-formyltriphenylamine; 4-formyltriphenylamine and 4-bromobenzene acetonitrile are subjected to Knoevenagel condensation reaction in an ethanol solution of sodium hydroxide to generate 2- (4-bromophenyl) -3- (4- (N, N-diamino) phenyl) -acrylonitrile; 2- (4-bromophenyl) -3- (4- (N, N-diamino) phenyl) -acrylonitrile and pinacol ester diboron are subjected to Miyaura Borylation reaction under the catalysis of bis (triphenylphosphine) palladium dichloride to generate a compound D3.
(4) When X represents phenylethynyl, the synthesized 4-iodotriphenylamine and trimethylsilylacetylene are subjected to Sonogashira coupling reaction under the catalysis of bis (triphenylphosphine) palladium dichloride-cuprous iodide together to generate N, N-diphenyl-4-trimethylsilylethynyl aniline; carrying out desilicication reaction on the N, N-diphenyl-4-trimethylsilylethynyl aniline under the alkaline condition of potassium carbonate to generate N, N-diphenyl-4-ethynylaniline; the preparation method comprises the following steps of carrying out Sonogashira coupling reaction on N, N-diphenyl-4-ethynylaniline and 4-bromoiodobenzene under the co-catalysis of bis (triphenylphosphine) palladium dichloride-cuprous iodide to generate 4- (2- (4-bromophenyl) ethynyl) -N, N-diphenylaniline; 4- (2- (4-bromophenyl) ethynyl) -N, N-diphenylaniline and pinacol ester diboron are subjected to Miyaura Borylation reaction under the catalysis of bis (triphenylphosphine) palladium dichloride to generate a compound D4.
The synthetic route of the above reaction is as follows:
example 1
This example discloses the synthesis of small organic molecule donor material Q1, comprising the following steps:
under the protection of nitrogen, compound A (0.25mmol,0.178g), compound D1(0.30mmol, 0.134g), tetrakis (triphenylphosphine) palladium (0.025mmol,29mg) and potassium carbonate (10mmol,1.380 g) were placed in a 50mL three-necked flask, 10mL of toluene, 5mL of ethanol and 5mL of water were sequentially added, and the mixture was heated under reflux at 110 ℃ for 48 hours. The reaction was cooled to room temperature, poured into 20mL of water and extracted with dichloromethane (3X 30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the crude product was subjected to column chromatography using petroleum ether/dichloromethane as the developing solvent in a volume ratio of 1:1 to give 0.143g of a red solid in 60.0% yield.
The reaction scheme above for the preparation of compound Q1 is as follows:
referring to fig. 1, there is shown a normalized uv-vis absorption spectrum of compound Q1 of example 1 in a chloroform solution and in a film-forming state. As can be seen, in the chloroform solution and thin film state, the compound Q1 shows two obvious characteristic absorption peaks in the range of 300-600nm, the absorption peak at the short wavelength is caused by the pi-pi transition in the molecule, and the absorption peak at the long wavelength is caused by the electron donating group and the electron withdrawing group in the molecular structureCaused by ICT interaction between radicals. Maximum absorption peak (. lamda.) of Compound Q1 in chloroform solutionmax sol) At 480 nm. In the solid state, the absorption range of the compound is widened due to intermolecular pi-pi stacking effect, and the maximum absorption wavelength peak (lambda) is generatedmax film) The red shift was to 495 nm. The optical bandwidth of compound Q1 was calculated from its absorption edge in the film-forming state
Is 2.12 eV.
Referring to FIG. 2, is Bu at 0.1M for compound Q1 in example 14NBF4/CH2Cl2Cyclic voltammograms measured in solution. As can be seen, the initial oxidation potential (E) of Compound Q1ox) And initial reduction potential (E)red) 0.54V, -1.44V, respectively, and their corresponding HOMOCVAnd LUMOCVRespectively-5.29 eV and-3.31 eV. At the same time, HOMOCV-LUMOCVThe difference of energy levels is forbidden band width
Is 1.98 eV.
Referring to FIG. 3, the compound Q1 of example 1 and PC61BM according to the mass ratio of 1: 3 (the total concentration is 12 mgmL)-1) The current-voltage curves of photovoltaic devices as active layers are mixed. Preliminary test results show that the photovoltaic performance of the device, i.e. J, is preliminarily obtained after the active layer is simply solution-suspendedscIs 6.58mA cm-2，Voc1.01V, a Fill Factor (FF) of 0.30 and a PCE of 2.02%.
Example 2
This example discloses the synthesis of small organic molecule donor material Q2, comprising the following steps:
under the protection of nitrogen, compound A (0.25mmol,0.178g), compound D2(0.30mmol, 0.142g), tetrakis (triphenylphosphine) palladium (0.025mmol,29mg) and potassium carbonate (10mmol,1.380 g) were placed in a 50mL three-necked flask, 10mL of toluene, 5mL of ethanol and 5mL of water were sequentially added, and the mixture was heated under reflux at 110 ℃ for 48 hours. The reaction was cooled to room temperature, poured into 20mL of water and extracted with dichloromethane (3X 30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the crude product was subjected to column chromatography using petroleum ether/dichloromethane in a volume ratio of 2: 1 as a developing solvent to give 0.159g of a red solid in 65.0% yield.
The reaction scheme above for the preparation of compound Q2 is as follows:
referring to fig. 4, the absorption chart of compound Q2 in chloroform solution and film-forming state is normalized uv-vis spectrum in example 2. As can be seen, compared with the compound Q1 in example 1, the maximum absorption of the compound Q2 in chloroform solution and solid state in example 2 is red-shifted, i.e. the compound Q2 is red-shifted due to the increased conjugation degree and the enhanced planarity of the molecules after the styryl group is introduced, namely
And
the wavelengths of the light wave are respectively expanded from 480nm and 495nm to 485nm and 501 nm. In addition, the calculation of the marginal absorption under the solid film gave the compound Q2
It was 2.07 eV.
Referring to FIG. 5, is Bu at 0.1M for compound Q2 in example 24NBF4/CH2Cl2Cyclic voltammograms measured in solution. As can be seen, E of the compound Q2oxAnd Ered0.40V and-1.42V, respectively, corresponding HOMOCVAnd LUMOCVRespectively-5.15 eV and-3.33 eV,
it was 1.82 eV. The introduction of styryl groups favoured the reduction of the material Q2 compared to the results of the electrochemical tests of the two compounds of example 1 and example 3
Referring to FIG. 6, the compound Q2 of example 2 and PC61BM according to the mass ratio of 1: 3 (the total concentration is 12 mgmL)-1) The current-voltage curves of photovoltaic devices as active layers are mixed. Preliminary test results show that after simple solution suspension coating, the photovoltaic performance of the device is as follows: j. the design is a squarescIs 5.92mA cm-2， Voc0.96V, FF 0.31, PCE 1.78%. Compound Q2 in example 2 has a relatively lower V than both compounds in example 1 and example 3ocValue that is relatively high HOMO for this compoundCVThe energy level value is relevant.
Example 3
This example discloses the synthesis of small organic molecule donor material Q3, comprising the following steps:
under the protection of nitrogen, compound A (0.25mmol,0.178g), compound D3(0.30mmol, 0.150g), tetrakis (triphenylphosphine) palladium (0.025mmol,29mg) and potassium carbonate (10mmol,1.380 g) were placed in a 50mL three-necked flask, 10mL of toluene, 5mL of ethanol and 5mL of water were sequentially added, and the mixture was heated under reflux at 110 ℃ for 48 hours. The reaction was cooled to room temperature, poured into 20mL of water and extracted with dichloromethane (3X 30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the crude product was subjected to column chromatography using petroleum ether/dichloromethane as the developing solvent in a volume ratio of 2: 3 to give 0.153g of a red solid in 61.0% yield.
The reaction scheme above for the preparation of compound Q3 is as follows:
referring to fig. 7, the absorption chart of compound Q3 in chloroform solution and film-forming state is normalized uv-vis spectrum. As can be seen, in comparison with the compounds of example 1, example 2 and example 4, in the range of 300-600nm, the absorption of the compound Q3 in example 3 at long wavelength is stronger than that at short wavelength in the solution and thin film state. This illustrates that compared to other bridgesThe bond, 2-cyano-styryl, has stronger electron withdrawing property, so that ICT effect in molecules is more obvious than other compounds. In addition, it is calculated from the edge absorption
Is 2.11 eV.
Referring to FIG. 8, is Bu at 0.1M for compound Q3 in example 34NBF4/CH2Cl2Cyclic voltammograms measured in solution. As can be seen, compound Q3 has an initial oxidation potential of 0.61V and an initial reduction potential of-1.38V, and the corresponding HOMOCVIs-5.36 eV, LUMOCVIs-3.37 eV, and,
is 1.99 eV. Compared to examples 1,2 and 4, the E of the compound is effectively increased due to the 2-cyano-styryl bridgeoxTo E thereofredThe reduction is not significant, resulting in the HOMO of Compound Q3 in example 3CVLower, it is predicted that the compound will achieve higher VocThe value is obtained.
Referring to FIG. 9, the compound Q3 of example 3 and PC61BM according to the mass ratio of 1: 3 (the total concentration is 12 mgmL)-1) The current-voltage curves of photovoltaic devices as active layers are mixed. Test results show that the photovoltaic performance of the device, namely J, is obtained primarily after the active layer is simply solution-suspendedscIs 7.96mA cm-2，Voc1.03V, FF 0.30, PCE 2.43%. The compound exhibited the highest V compared to the compounds in the other examplesocThis is due to its lower HOMOCVEnergy level value, which is the highest V of the existing solution process based on triphenylamine-benzothiadiazole asymmetric organic small molecule donor materialoc. In addition, J of the materialscAnd also reaches the highest, which is related to the fact that the ultraviolet-visible spectrum absorption chart shows stronger ICT peaks, and further high PCE is obtained.
Example 4
This example discloses the synthesis of small organic molecule donor material Q4, comprising the following steps:
under the protection of nitrogen, compound A (0.25mmol,0.178g), compound D4(0.30mmol, 0.141g), tetrakis (triphenylphosphine) palladium (0.025mmol,29mg) and potassium carbonate (10mmol,1.380 g) were placed in a 50mL three-necked flask, 10mL of toluene, 5mL of ethanol and 5mL of water were sequentially added, and the mixture was heated under reflux at 110 ℃ for 48 hours. The reaction was cooled to room temperature, poured into 20mL of water and extracted with dichloromethane (3X 30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the crude product was subjected to column chromatography using petroleum ether/dichloromethane as the developing solvent in a volume ratio of 3: 2 to give 0.125g of a red solid in 51.2% yield.
The reaction scheme above for the preparation of compound Q4 is as follows:
referring to fig. 10, the absorption chart of compound Q4 in chloroform solution and film-forming state is normalized uv-vis spectrum in example 4. As can be seen from the figure, similar to the compound absorptions in example 1 and example 2, the compound Q4 in example 4 has two distinct characteristic absorption peaks in the range of 300-600nm in both the solution state and the thin film state. After the phenylethynyl is introduced into the molecular structure, the aim of increasing the molecular conjugation degree and improving the molecular planarity is also fulfilled, so that the maximum absorption peak of the compound Q4 in example 4 is red-shifted by 15 nm. However, since C ≡ C is slightly more rigid than C ≡ C, the backbone structure of the molecule is distorted to some extent, resulting in a slight blue-shift in its absorption compared to compound Q2 in example 2, but compound Q4
Narrower than compound Q2, 2.05 eV.
See FIG. 11 for Bu at 0.1M for Compound Q4 in example 44NBF4/CH2Cl2Cyclic voltammograms measured in solution. As can be seen, compound Q4 has an initial oxidation potential of 0.43V and an initial reduction potential of-1.43V, and the corresponding HOMOCVIs-5.18 eV, LUMOCVIs-3.32 eV, and is,
it was 1.86 eV. Compared with the compound Q1 in example 1, the introduction of phenylethynyl effectively reduces HOMO of the material Q4CVTo LUMOCVThe influence is not great. In addition, compared with compound Q2 in example 2, since C ≡ C is more electronegative than C ═ C, it results in a HOMO towards the compoundCVThe reduction degree of (D) is slightly larger than that of LUMOCVIs reduced, then
Slightly wider than compound Q2. In addition, in comparison with the compound Q3 in example 3, phenylethynyl group is weaker in electron-withdrawing ability than 2-cyano-styryl group, and thus HOMO thereofCVHigher than compound Q3. In addition, of Compound Q4 in this example
It was 1.86 eV.
See FIG. 12 for a series of experiments with the compound Q4 of example 4 and PC61BM according to the mass ratio of 1: 3 (the total concentration is 12 mgmL)-1) The current-voltage curves of photovoltaic devices as active layers are mixed. Test results show that after the active layer is simply subjected to solution suspension coating, the photovoltaic performance of the device obtained preliminarily is as follows: j. the design is a squaresc＝5.91mA cm-2，Voc0.94V, FF 0.27, PCE 1.48%. Compared with the compounds in other examples, the rigidity of phenylethynyl is stronger than that of other bridges, so that the whole skeleton of the molecule Q4 is slightly distorted, and relatively weak absorption capacity, JscSlightly decreased.
The photophysical, electrochemical and photovoltaic data for the compounds synthesized in examples 1-4 are listed in Table 1.
As can be seen from Table 1, the compounds Q1 to Q4 of the examples of the present invention
And
the change trend of the pressure sensor is basically consistent. Compared with the other two bridge bonds, after the phenyl and the phenylethynyl are introduced, the HOMO energy level of the corresponding compound is effectively reduced, and then high V exceeding 1.0V is obtainedoc. Compared with the prior literature, the micromolecule donor materials synthesized by the method all show more outstanding photovoltaic performance, and particularly, a photovoltaic device taking the compound Q3 as the micromolecule donor obtains a high V of 1.03VocAnd a PCE of 2.43%. The result is that the solution process reported in the literature at present is based on the highest V of the benzothiadiazole-triphenylamine asymmetric organic small molecule donor materialoc。
Claims (4)
1. A benzothiadiazole asymmetric organic micromolecule photovoltaic material has the following specific structure:
wherein X is a bond selected from
R is selected from alkyl of C1-C8.
2. The preparation method of the benzothiadiazole asymmetric organic small molecule photovoltaic material as claimed in claim 1, which comprises the following steps:
the synthesis strategy is as follows:
wherein X is a bond selected from
R is selected from alkyl of C1-C8;
under the protection of nitrogen, the compound A and the compound D are put into a Suzuki cross-coupling reaction system catalyzed by palladium according to the equivalent ratio of 1:2.2, the reaction is carried out at 110 ℃, the reaction time is 48 hours, and the crude product is separated and purified by column chromatography to obtain the organic micromolecule Q.
3. The method for preparing the benzothiadiazole asymmetric organic small molecule photovoltaic material according to claim 2, characterized in that: in a Suzuki coupling reaction system, tetrakis (triphenylphosphine) palladium is used as a catalyst, and potassium carbonate is used as alkali; the equivalent ratio of the compound A to the potassium carbonate is 1: 40; the equivalent ratio of catalyst to compound a was 1: 10.
4. The benzothiadiazole-based asymmetric small organic molecule photovoltaic material of claim 1 as a donor, [6,6 ] or]-phenyl-C61-butyric acid methyl ester (PC)61BM) is an application of an acceptor in preparing an active layer of an organic small-molecule solar cell device.
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| CN103998445A (en) * | 2011-08-08 | 2014-08-20 | 艾尼股份公司 | Process for the preparation of benzohetero[1,3]diazole compounds disubstituted with heteroaryl groups |
| KR20150086737A (en) * | 2014-01-20 | 2015-07-29 | 공주대학교 산학협력단 | triphenylamine-benzothiadiazole derivative compound and organic solar cell having photoactive layer including the same |
| CN105237524A (en) * | 2015-11-06 | 2016-01-13 | 大连理工大学 | Benzotriazole unit-containing linear (D-pi-A-pi)2-D organic micro-molecular photovoltaic material, and preparation method and application thereof |
| CN105348274A (en) * | 2015-11-27 | 2016-02-24 | 大连理工大学 | Benzotriazole small-organic-molecule photovoltaic material and preparation method and application thereof |
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