CN108383853B - A kind of donor material based on fluorine-containing Oxoindole and preparation method thereof and device - Google Patents
A kind of donor material based on fluorine-containing Oxoindole and preparation method thereof and device Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000011737 fluorine Substances 0.000 title claims abstract description 12
- QNLOWBMKUIXCOW-UHFFFAOYSA-N indol-2-one Chemical compound C1=CC=CC2=NC(=O)C=C21 QNLOWBMKUIXCOW-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 47
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 32
- -1 aldehyde radical end group compound Chemical class 0.000 claims description 21
- 229930192474 thiophene Natural products 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 8
- 125000001246 bromo group Chemical group Br* 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- SCRXASNUPJPFGP-UHFFFAOYSA-N 1-fluoro-3h-indol-2-one Chemical compound C1=CC=C2N(F)C(=O)CC2=C1 SCRXASNUPJPFGP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 150000003053 piperidines Chemical class 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical compound N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 claims description 2
- YNTQKXBRXYIAHM-UHFFFAOYSA-N azanium;butanoate Chemical compound [NH4+].CCCC([O-])=O YNTQKXBRXYIAHM-UHFFFAOYSA-N 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- UGYRYNXDEOFIQB-UHFFFAOYSA-N benzene thiophene Chemical compound S1C=CC=C1.C1=CC=CC=C1.C1=CC=CC=C1 UGYRYNXDEOFIQB-UHFFFAOYSA-N 0.000 claims 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000004528 spin coating Methods 0.000 abstract description 5
- 238000013086 organic photovoltaic Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 description 9
- 238000000137 annealing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004847 absorption spectroscopy Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 2
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 101100481028 Arabidopsis thaliana TGA2 gene Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NAFKATGXNZPPOC-UHFFFAOYSA-N N(=C=S)[SiH2][N+](=O)[O-] Chemical compound N(=C=S)[SiH2][N+](=O)[O-] NAFKATGXNZPPOC-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 125000005631 S-sulfonamido group Chemical group 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000013083 solar photovoltaic technology Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses the donor material based on fluorine-containing Oxoindole, general formula of the chemical structure is as follows:, the organic photoelectrical material synthesis step is simple, it is easy purifying, structure determination, and with the organic photovoltaic devices of the organic donor material preparation in the present invention, without cumbersome post-processing, the thick devices with high light electrotransformation efficiency only can be obtained by simple solution spin coating, and active layer thickness range can tolerate variation within the scope of 120nm-230nm, its incident photon-to-electron conversion efficiency may remain between 5.3%-7.8%, highest optoelectronic transformation efficiency can be up to 7.80%, potentiality and good application value with " roll-to-roll " preparation or printing preparation large area photovoltaic device.
Description
Technical field
This application involves solar cell material field, especially a kind of donor material based on fluorine-containing Oxoindole and its
Preparation method and device.
Background technique
Solar energy is one of ideal alternative energy source most safe, most green, most environmentally friendly at present, and solar-photovoltaic technology is also
One of the important channel of fossil energy crisis is solved at present.Compared with traditional inorganic silicon-based solar battery, organic solar
Battery has many advantages, such as light weight, at low cost, solution-processible, high mechanical flexibility, can be made into large area flexible device, by
Favor, the development advanced by leaps and bounds in recent years.Nevertheless, cumbersome device optimization process (such as additive, thermal annealing
Or solvent anneal etc.) due to the high difficulty that it accurately controls pattern, it is repeatable to result in the extremely low batch of Efficient devices
Property.In addition to this, the active layer production of device is partially thin at present, and change in film thickness tolerance is very low, generally needs accurately
Controlling it, higher transfer efficiency just can be achieved with a thickness of 100nm or less, in device preparation " roll-to-roll "
Or the application of inkjet printing technology, and the preparation of novel donor material is vital for the improvement of the above phenomenon.
Summary of the invention
The purpose of the present invention is analyzing in view of the above technology, a kind of organic photoelectric compound, the organic photoelectrical material are provided
Preparation step is simple, is easy purifying, structure determination, with the organic photovoltaic devices of the organic photoelectrical material preparation in the present invention, nothing
Cumbersome optimal conditions (such as additive, thermal annealing or solvent anneal etc.) are needed, only can be obtained by simple solution spin coating
The thick devices of incident photon-to-electron conversion efficiency with higher.
Technical solution of the present invention:
A kind of organic photoelectric compound, is made of big organic conjugate unit system and alkane or class alkane structure, for tool
There is the dark green solid powder of metallic luster, the general formula of the chemical structure of compound is as follows:
Wherein:
R1Selected from H, C1-C8Alkyl, C1-C8Alkyl substituent, C3-C8Naphthenic base, C3-C8Naphthenic substituent, C1-C8Alcoxyl
Base, R2-R5The derivative that respectively H, halogenated or its halogen replace, the halogen mean bromine, chlorine, fluorine or iodine, R2-R5It can phase
It is same to can also be different；R6-R8Respectively H, C1-C30Alkyl, C1-C30Alkyl substituent, C3-C30Naphthenic base, C3-C30Naphthenic base takes
Dai Ji, C1-C30Alkoxy, C1-C30Alkylthio group, halogenated C1-C30Alkyl, halogenated C3-C30Naphthenic base or halogenated C1-C30Alkoxy,
And R6And R7It can be the same or different；Alkyl group can be it is any substituted that is, substituted or unsubstituted, when being taken
Dai Shi, substituent group are individually and one or more group independently selected from the following: naphthenic base, aryl, heteroaryl, miscellaneous
Alcyl, hydroxyl, alkoxy, aryloxy group, sulfydryl, alkylthio group, arylthio, cyano, halogenated, carbonyl, thiocarbonyl, O- amino first
Acyl group, N- carbamoyl, O- thiocarbamoyl, N- thiocarbamoyl, C- acylamino-, N- acylamino-, the Asia S- sulphur
Acylamino-, N- sulfonamido, C- carboxyl, O- carboxyl, isocyanato-, thiocyano, isothiocyanato, nitro, monosilane
Base, three halide sulfonyls ,-NR ' R " or amino including mono- and di- substituted amino group and its protected
Derivative；Group of naphthene base can be any substituted that is, substituted or unsubstituted；When substituted, substituent group is single
Solely and one or more group independently selected from the following: naphthenic base, aryl, heteroaryl, heteroalicyclyl, hydroxyl, alcoxyl
Base, aryloxy group, sulfydryl, alkylthio group, arylthio, cyano, halogenated, carbonyl, thiocarbonyl, O- carbamoyl, N- carbamyl
Base, O- thiocarbamoyl, N- thiocarbamoyl, C- acylamino-, N- acylamino-, S- sulfonamido, N- sulfenyl
Amino, C- carboxyl, O- carboxyl, isocyanato-, thiocyano, isothiocyanato, nitro, silicyl, three halide sulphurs
Acyl group ,-NR ' R " or amino and its protected derivative including mono- and di- substituted amino group；
N and m takes 1 to 50 positive integer, and n and m can be the same or different；
The organic photoelectric compound, structural formula are as follows:
Wherein, R1Selected from H, C1-C8Alkyl, C1-C8Alkyl substituent, C3-C8Naphthenic base, C3-C8Naphthenic substituent, C1-
C8Alkoxy, R2-R4Separately it is selected from H, C1-C30Alkyl, C1-C30Alkyl substituent, C3-C30Naphthenic base, C3-C30Cycloalkanes
Base substituent group, C1-C30Alkoxy, C1-C30Alkylthio group, halogenated C1-C30Alkyl, halogenated C3-C30Naphthenic base or halogenated C1-C30Alcoxyl
Base, wherein R2And R3It can be the same or different.
The organic photoelectric compound, structural formula are as follows:
The preparation method of the donor material, by the way that dialdehyde cardinal extremity based compound and fluorine-containing Oxoindole end group is precursor
Object is closed to carry out Ke Neifeinageer (Knoevenagel) condensation reaction and be made, comprising the following steps:
1) under protection of argon gas, by bromo list aldehyde radical end group compound and the double tin of the alkyl-substituted benzene thiophene of thiophene
Monomer, solvent a n,N-Dimethylformamide and the mixing of catalyst a tetra-triphenylphosphine palladium, heating reflux reaction 1-7 days, with dichloro
Methane-petroleum ether is eluant, eluent, and column chromatography for separation obtains intermediate double aldehyde radical end group compound；The bromo list aldehyde radical end group
Compound is 5 "-bromo- 3,3 ",-dioctyl-[2,2':5', 2 "-four thiophene] -5- aldehyde；
The structure of the double tin monomers of the alkyl-substituted benzene thiophene of thiophene are as follows:
2) above-mentioned dialdehyde cardinal extremity based compound, fluorine-containing Oxoindole end group precursor compound, solvent b and catalyst b are mixed
It closes, under argon gas protection, is heated to reflux 24 hours, with chloroform extraction, merge organic phase, anhydrous sodium sulfate is dry, and decompression removes
Solvent is removed, organic photoelectric compound is made in column chromatography for separation；
The structural formula of the dialdehyde cardinal extremity based compound is as follows:
Fluorine-containing Oxoindole end group precursor compound is the fluoro- 1,3- dihydro -2H- indol-2-one of 1- ethyl -5,6- two.
The preparation method of the donor material, bromo list aldehyde radical end group compound and the alkyl-substituted benzene thiophene of thiophene
The mass ratio of double tin monomers is 2:1, solvent a n,N-Dimethylformamide and the double tin of the alkyl-substituted benzene thiophene of thiophene
Change monomer amount ratio be 10-100 liter/mole, catalyst a Pd (PPh3)4With the double tin of the alkyl-substituted benzene thiophene of thiophene
The molar ratio for changing monomer is 0.1-20:100.
The preparation method of the donor material, the solvent b are in chloroform, chloroform, methylene chloride and tetrahydrofuran
One or more kinds of arbitrary proportions mixture；The amount ratio of solvent b and dialdehyde cardinal extremity based compound is 10-30 liter/rub
You.
The preparation method of the donor material, the catalyst b be one or both of triethylamine, pyridine and piperidines with
The mixing of one or more of the mixture and ammonium acetate of upper arbitrary proportion, propionic acid ammonium and butyric acid ammonium arbitrary proportion
Object；The molar ratio of catalyst b and dialdehyde cardinal extremity based compound is 2:10.
A kind of solar cell photovoltaic device: the activity using the donor material as solar cell photovoltaic device
Layer.
The invention has the advantages that the organic photoelectrical material synthesis step is simple, is easy purifying, structure determination, and with this hair
The organic photovoltaic devices of organic donor material preparation in bright, without cumbersome post-processing (such as additive, thermal annealing or solvent
Annealing etc.), the thick devices with high light electrotransformation efficiency, and active thickness only can be obtained by simple solution spin coating
Degree range can tolerate 120nm-230nm within the scope of variation, incident photon-to-electron conversion efficiency may remain in 5.3%-7.8% it
Between, highest optoelectronic transformation efficiency can be up to 7.80%, the potentiality with " roll-to-roll " preparation or printing preparation large area photovoltaic device
With good application value.
Detailed description of the invention
Fig. 1 is the ultraviolet-visible absorption spectroscopy of compound solution prepared by embodiment 1 and film.
Fig. 2 is current density voltage curve of the compound of the preparation of embodiment 1 under optimal device conditions.
Fig. 3 is thermogravimetric analysis (TGA) curve of compound prepared by embodiment 1.
Fig. 4 is differential scanning calorimetry (DSC) curve of compound prepared by embodiment 1.
Specific embodiment
In the following description, including certain concrete details are to provide comprehensive reason to each disclosed embodiment
Solution.However, those skilled in the relevant art are not, it will be recognized that use one or more of these concrete details, and use other
Embodiment can be achieved in the case where method, component, material etc..
Embodiment 1:
A kind of organic photoelectric compound, is made of big organic conjugate unit system and alkane or class alkane structure, for tool
There is the dark green solid powder of metallic luster, the general formula of the chemical structure of compound is as follows:
Wherein: R1For ethyl, R2And R3For fluorine atom, R4And R5For n-octyl, R6For 2- ethylhexyl, i.e. the compound
Chemical structural formula are as follows:
This for solar battery organic photoelectric compound preparation method, by by dialdehyde cardinal extremity based compound with contain
Fluorine Oxoindole end group precursor compound carries out Ke Neifeinageer (Knoevenagel) condensation reaction and is made, including following
Step:
1) under protection of argon gas, by 5 "-bromo- 3,3 ",-dioctyl-[2,2':5', 2 "-four thiophene] -5- aldehyde 3.85g
(6.63mmol) and the alkyl-substituted benzene thiophene of thiophene double tin monomer 3.00g (3.32mmol), 60mL dry N, N- bis-
Methylformamide and tetra-triphenylphosphine palladium 0.20g (0.17mmol) mixing, heating reflux reaction 1 day, then pour into reaction solution
It in 100mL water, is extracted 3 times with 40mL methylene chloride, organic phase is with 50mL water washing 3 times, and after anhydrous sodium sulfate is dry, decompression is removed
N,N-Dimethylformamide is gone, using dichloromethane-petroleum ether as eluant, eluent, intermediate double aldehyde radical end group is made in column chromatography for separation
Compound, structural formula are as follows:
2) by above-mentioned dialdehyde cardinal extremity based compound 1.00g (0.63mmol), 1- ethyl -5,6- two in 100mL bottle with two necks
Fluoro- 1,3- dihydro -2H- indol-2-one 1.25g (6.34mmol), dry chloroform 150mL and piperidines 0.01g
(0.05mmol) mixing is heated to reflux 24 hours under argon gas protection, with chloroform extraction, merges organic phase, anhydrous sodium sulfate
It is dry, solvent is removed under reduced pressure, metallic luster dark green solid, that is, organic photoelectric compound 1.00g, yield is made in column chromatography for separation
It is 81.5%.1H NMR (500MHz, CDCl3) δ 7.61 (dd, J=13.8,6.0Hz, 3H), 7.46 (dd, J=48.1,
23.7Hz, 2H), 7.34-7.28 (m, 4H), 7.12 (s, 4H), 6.95 (d, J=3.2Hz, 2H), 6.81-6.64 (m, 2H),
3.91-3.78 (m, 6H), 2.93-2.75 (m, 18H), 1.71 (d, J=6.9Hz, 16H), 1.51-1.20 (m, 100H), 0.98
(dd, J=18.9,11.5Hz, 16H), 0.88 (t, J=6.3Hz, 14H) .HRMS (MALDI-TOF): m/z calcd for
C112H132F4N2O2S10:1934.90.Found:1930.596[M]+.
The test method of the ultraviolet-visible absorption spectroscopy of compound obtained:
Organic photoelectric compound obtained is made into 10 respectively-5Mol/L and 10-2The chloroformic solution of mol/L, former solution
For measuring solution UV absorption, the latter solution in 1200rpm on quartz plate after rejection film, for measuring the UV absorption of film,
Scanning range is 300-900 nanometers, measuring instrument SHIMADZUUV-1750.Ultraviolet-visible absorption spectroscopy is as shown in Figure 1.
The solution of the compound has good absorption in the range of 300-800 nanometers, and film has more than 59 nanometers relative to solution
Red shift, and there is wider absorption region, it help to obtain higher incident photon-to-electron conversion efficiency.
The test method of the thermogravimetric analysis of compound obtained:
By organic photoelectric compound obtained in a vacuum drying oven it is dry for 24 hours, remove remaining a small amount of organic solvent and
Water weighs 3mg in ceramic crucible, carries out thermogravimetric analysis, journey on thermogravimetric analyzer METTLER TOLEDO TGA2 after dry
Sequence gas is nitrogen, flow 50mL/min.The temperature range of measurement is 30-600 DEG C.
The test method of the differential scanning calorimetric curve of compound obtained:
By organic photoelectric compound obtained in a vacuum drying oven it is dry for 24 hours, remove remaining a small amount of organic solvent and
Water weighs 3mg in aluminum cup, using the dress sample loading mode for covering punching, in analyzer NETZSCH after dry
Differential scanning calorimetric analysis is carried out on DSC214Polym, purge gass and protection gas are nitrogen, and flow is respectively 40mL/min
And 60mL/min.The temperature range of measurement is 30-300 DEG C.
The preparation of solar cell device is used for using organic photoelectric compound obtained as electron donor:
Device architecture is ITO/PEDOT:PSS/ donor molecule: PC71BM/PFN-Br/Al.Specific preparation process are as follows: first
ITO (tin indium oxide, anode) glass is pre-processed, the specific steps are as follows: first by ito glass successively with dish washing liquid, go
Ionized water, acetone, isopropanol solvent are cleaned by ultrasonic each 20 minutes, are dried up after taking-up with nitrogen gun, and UV-Ozone handles 30min.
Then one layer of PEDOT:PSS (CleviosPVPAl4083) of spin coating is used as anode modification layer on pretreated ito glass, to
PEDOT:PSS dries 10 minutes at 150 DEG C in an oven, the compound and PC for preparing embodiment 1 after cooling71The mixture of BM
Chloroformic solution is spin-coated on the surface PEDOT:PSS as active layer, then carries out thermal annealing and solvent vapo(u)r annealing, spin coating with a thickness of
The methanol solution of the PFN-Br of 10nm, last evaporation thickness are the metal electrode Al of 100nm.Vacuum degree is kept during vapor deposition
Lower than 2 × 10-6Pa.Under standard sunlight (AM1.5G) radiation parameter, keep the Keithley2400 to computerized control digital
Source table tests device performance, and performance parameter is listed in table 1-3.
Table 1: compound is compared to/receptor than the solar cell properties of preparation with difference
(light intensity 100mW/cm2It is measured under AM1.5G irradiation condition)
Table 2: compound is compared with solar cell properties prepared by different activities thickness degree
(light intensity 100mW/cm2It is measured under AM1.5G irradiation condition)
Table 3: compound is compared with solar cell properties prepared by different interfaces
(light intensity 100mW/cm2It is measured under AM1.5G irradiation condition)
Fig. 2 is current density voltage curve of the compound of the preparation of embodiment 1 under optimal device conditions, is shown in figure:
Open-circuit voltage (the V of the corresponding battery of organic solar batteries optimised devices based on compoundoc) it is 0.84V, short circuit current is close
Spend (Jsc) it is 13.0mA/cm2, fill factor (FF) is 71.8%, and it is high performance that photoelectric conversion efficiency (PCE), which is 7.80%,
Organic solar batteries.
In conclusion using the compounds of this invention preparation solution processing bulk heterojunction solar cells device without
It post-processes (such as additive, thermal annealing or solvent anneal etc.), can be obtained the thick devices with preferable photovoltaic performance,
Maximum photoelectric conversion efficiency can reach 7.80%.And the active layer prepared using the compound of the present invention, thickness range can
Changed with tolerating within the scope of 120nm-230nm, incident photon-to-electron conversion efficiency may remain between 5.3%-7.8%, have " volume
To volume " prepare or print the potentiality and good application value that prepare large area photovoltaic device.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (6)
1. a kind of donor material based on fluorine-containing Oxoindole, which is characterized in that structural formula are as follows:
2. a kind of preparation method of donor material as described in claim 1, it is characterised in that: by by dialdehyde cardinal extremity based compound
Ke Neifeinageer (Knoevenagel) condensation reaction is carried out with fluorine-containing Oxoindole end group precursor compound and is made, including
Following steps:
1) under protection of argon gas, by bromo list aldehyde radical end group compound and the double tin lists of the alkyl-substituted benzene thiophene of thiophene
Body, solvent a n,N-Dimethylformamide and the mixing of catalyst a tetra-triphenylphosphine palladium, heating reflux reaction 1-7 days, with dichloromethane
Alkane-petroleum ether is eluant, eluent, and column chromatography for separation obtains intermediate double aldehyde radical end group compound；The bromo list aldehyde radical end group
Closing object is 5 "-bromo- 3,3 ",-dioctyl-[2,2':5', 2 "-four thiophene] -5- aldehyde；
The structure of the double tin monomers of the alkyl-substituted benzene thiophene of thiophene are as follows:
2) above-mentioned dialdehyde cardinal extremity based compound, fluorine-containing Oxoindole end group precursor compound, solvent b and catalyst b are mixed, argon
It under gas shielded, is heated to reflux 24 hours, with chloroform extraction, merges organic phase, anhydrous sodium sulfate is dry, is removed under reduced pressure molten
Organic photoelectric compound is made in agent, column chromatography for separation；
The structural formula of the dialdehyde cardinal extremity based compound is as follows:
Fluorine-containing Oxoindole end group precursor compound is the fluoro- 1,3- dihydro -2H- indol-2-one of 1- ethyl -5,6- two.
3. the preparation method of donor material according to claim 2, it is characterised in that: bromo list aldehyde radical end group compound and thiophene
The mass ratio of the double tin monomers of the benzene thiophene that alkylated phenothiazine replaces is 2:1, solvent a n,N-Dimethylformamide and thiophane
The amount ratio of the double tin monomers of the benzene thiophene that base replaces be 10-100 liter/mole, catalyst a Pd (PPh3)4With thiophane
The molar ratio of the double tin monomers of the benzene thiophene that base replaces is 0.1-20:100.
4. the preparation method of donor material according to claim 2, it is characterised in that: the solvent b is chloroform, three chloromethanes
The mixture of one or more of alkane, methylene chloride and tetrahydrofuran arbitrary proportion；Solvent b and dialdehyde cardinal extremity base chemical combination
The amount ratio of object be 10-30 liter/mole.
5. the preparation method of donor material according to claim 2, it is characterised in that: the catalyst b is triethylamine, pyridine
With one of the mixture of one or more of piperidines arbitrary proportion and ammonium acetate, propionic acid ammonium and butyric acid ammonium or
The mixture of two or more arbitrary proportions；The molar ratio of catalyst b and dialdehyde cardinal extremity based compound is 2:10.
6. a kind of solar cell photovoltaic device, it is characterised in that: using donor material described in claim 1 as solar-electricity
The active layer of pond photovoltaic device.
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