CN117567513A - Self-assembled monolayer hole transport material containing bisphosphonic acid terminal group, preparation method and application - Google Patents
Self-assembled monolayer hole transport material containing bisphosphonic acid terminal group, preparation method and application Download PDFInfo
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- CN117567513A CN117567513A CN202311517206.7A CN202311517206A CN117567513A CN 117567513 A CN117567513 A CN 117567513A CN 202311517206 A CN202311517206 A CN 202311517206A CN 117567513 A CN117567513 A CN 117567513A
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- bisphosphonic acid
- assembled monolayer
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- 239000013545 self-assembled monolayer Substances 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 60
- 230000005525 hole transport Effects 0.000 title claims abstract description 42
- 239000002094 self assembled monolayer Substances 0.000 title claims abstract description 42
- 239000002253 acid Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000010410 layer Substances 0.000 claims abstract description 32
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- -1 cyano, methyl Chemical group 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 21
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 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 10
- JQPFYXFVUKHERX-UHFFFAOYSA-N 2-hydroxy-2-cyclohexen-1-one Natural products OC1=CCCCC1=O JQPFYXFVUKHERX-UHFFFAOYSA-N 0.000 claims description 9
- PEIKTSJIUKYDPC-UHFFFAOYSA-N Diethyl 3-Bromopropylphosphonate Chemical compound CCOP(=O)(OCC)CCCBr PEIKTSJIUKYDPC-UHFFFAOYSA-N 0.000 claims description 9
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- LJSFAWDWYVZQBG-UHFFFAOYSA-N 1-bromo-4-diethoxyphosphorylbutane Chemical compound CCOP(=O)(OCC)CCCCBr LJSFAWDWYVZQBG-UHFFFAOYSA-N 0.000 claims description 8
- 229940126062 Compound A Drugs 0.000 claims description 8
- 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 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012312 sodium hydride Substances 0.000 claims description 8
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 6
- FCSKOFQQCWLGMV-UHFFFAOYSA-N 5-{5-[2-chloro-4-(4,5-dihydro-1,3-oxazol-2-yl)phenoxy]pentyl}-3-methylisoxazole Chemical compound O1N=C(C)C=C1CCCCCOC1=CC=C(C=2OCCN=2)C=C1Cl FCSKOFQQCWLGMV-UHFFFAOYSA-N 0.000 claims description 6
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 150000004867 thiadiazoles Chemical class 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000004873 anchoring Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 72
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 238000006467 substitution reaction Methods 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 239000012267 brine Substances 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000000137 annealing Methods 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000004809 thin layer chromatography Methods 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000013082 photovoltaic technology Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 101100132433 Arabidopsis thaliana VIII-1 gene Proteins 0.000 description 2
- 101100459319 Arabidopsis thaliana VIII-2 gene Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- RGGOWBBBHWTTRE-UHFFFAOYSA-N (4-bromophenyl)hydrazine;hydron;chloride Chemical compound Cl.NNC1=CC=C(Br)C=C1 RGGOWBBBHWTTRE-UHFFFAOYSA-N 0.000 description 1
- YQVZREHUWCCHHX-UHFFFAOYSA-N (4-chlorophenyl)hydrazine;hydron;chloride Chemical compound Cl.NNC1=CC=C(Cl)C=C1 YQVZREHUWCCHHX-UHFFFAOYSA-N 0.000 description 1
- FQHCPFMTXFJZJS-UHFFFAOYSA-N (4-methoxyphenyl)hydrazine;hydrochloride Chemical compound Cl.COC1=CC=C(NN)C=C1 FQHCPFMTXFJZJS-UHFFFAOYSA-N 0.000 description 1
- RGXGEFSBDPGCEU-UHFFFAOYSA-N 1,4-dibromo-2,3-difluorobenzene Chemical compound FC1=C(F)C(Br)=CC=C1Br RGXGEFSBDPGCEU-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- JOVOSQBPPZZESK-UHFFFAOYSA-N phenylhydrazine hydrochloride Chemical compound Cl.NNC1=CC=CC=C1 JOVOSQBPPZZESK-UHFFFAOYSA-N 0.000 description 1
- 229940038531 phenylhydrazine hydrochloride Drugs 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
-
- 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
-
- 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)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
A self-assembled monolayer hole transport material containing biphosphonic acid terminal group, and its preparation method and application are provided. The hole transport material has a structural formula shown in a general formula A. The compound provided by the invention has a bisphosphonic acid terminal anchoring group, so that firm self-assembly can be generated with the surface of a substrate in a chemical bonding mode, and the compound has good coverage rate; meanwhile, the rigid conjugate large-plane condensed ring core structure ensures the hole transmission performance of the material and is beneficial to improving the photovoltaic performance of the material. The synthesis method has the characteristics of few reaction steps, low-cost and easily available raw materials, and low cost. The material is used as a hole transport material and applied to an inversion perovskite solar cell and a positive type perovskite solar cellIn organic solar cells, one can obtain>22% and>photoelectric conversion efficiency of 19%; as NiO x Application of modification layer material in inversion perovskite solar cell>The photoelectric conversion efficiency of 22% has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of photovoltaic materials, and relates to preparation and application of a self-assembled monolayer hole transport material containing bisphosphonic acid.
Background
Photovoltaic technology, which converts solar energy into electrical energy, is the most reasonable and efficient way to utilize solar energy, helping humans get rid of the reliance on traditional fossil energy sources. Organic Solar Cells (OSCs) and Perovskite Solar Cells (PSCs) have been rapidly developed in recent years as third generation photovoltaic technologies, and their Photoelectric Conversion Efficiencies (PCEs) have been rapidly increased to 19.8% and 26.1%, respectively. PSCs are used as the most commercially desirable third-generation photovoltaic technology at present, the stability and the service life of the device are one of important factors for limiting the development of the PSCs, and the inversion PSCs have greater advantages in the aspects of device stability, low hysteresis, low-temperature large-scale manufacturing and the like, so that the commercialization process of the PSCs is expected to be promoted. One major key to the current constraint on the efficiency of inverse PSCs is the Hole Transport Materials (HTMs), the most widely used HTM currently being poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA), which prevents further increases in efficiency of inverse PSCs due to its high cost, low hole mobility, poor wettability to perovskite precursors, and energy level mismatch. OSCs have great application prospect in wearable and special equipment because of flexible preparation and low cost. The high efficiency OSCs of >19% reported today are mostly based on positive structures, but the stability of such devices is poor, because the weakly acidic HTM poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT/PSS) used attacks the Indium Tin Oxide (ITO) electrode.
Despite the current development of HTMs based on either inverted PSCs or forward OSCs, the material costs are still high and not suitable for large-scale manufacturing and cannot be used for commercialization. In recent years, researchers have found that the use of self-assembled monolayer materials (SAMs) as HTMs is expected to solve this key problem. The advantages of the material are mainly as follows: (1) The SAM molecules are simple to synthesize and have extremely small dosage, thereby being beneficial to reducing the cost; (2) SAM molecules can be chemically bonded with the substrate, and the stability is high; (3) The SAM film can be prepared by soaking and other methods, which is beneficial to realizing high-flux and low-cost manufacture; (4) As HTMs, the SAM film has a small thickness, which is advantageous in reducing the series resistance and improving the battery efficiency. Therefore, development of SAM with excellent performance through molecular engineering design is expected to obtain HTMs with low cost and high efficiency, and promote commercialization of PSCs and OSCs.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a self-assembled monolayer hole transport material containing a bisphosphonic acid terminal group and a preparation method thereof, and the material can be applied to the fields of positive OSCs and negative PSCs.
The technical proposal of the invention
The self-assembled monolayer hole transport material containing the bisphosphonic acid terminal group provided by the invention has a structural formula shown in a general formula A:
wherein:
R 1 hydrogen, fluorine, chlorine, bromine, cyano, methyl, trifluoromethyl or methoxy;
R 2 is hydrogen, fluoro, cyano or a condensed substituted thiadiazole;
n is 3 or 4.
The self-assembled monolayer hole transport material containing the bisphosphonic acid terminal group can be specifically the following compounds: (indolo [2,3-a ] carbazole-11, 12-diylbis (prop-1, 3-diyl)) bisphosphonic acid (A-1), (3, 8-difluoroindolo [2,3-a ] carbazole-11, 12-diylbis (prop-1, 3-diyl)) bisphosphonic acid (A-2), (3, 8-dichloroindolo [2,3-a ] carbazole-11, 12-diylbis (but-1, 4-diyl)) bisphosphonic acid (A-3), (3, 8-dibromoindolo [2,3-a ] carbazole-11, 12-diylbis (prop-1, 3-diyl)) bisphosphonic acid (A-4) (3, 8-dibromoindolo [2,3-a ] carbazole-11, 12-diylbis (butan-1, 4-diyl)) bisphosphonic acid (A-5), (3, 8-dimethoxyindolo [2,3-a ] carbazole-11, 12-diylbis (butan-1, 4-diyl)) bisphosphonic acid (A-6), (5, 6-difluoroindolo [2,3-a ] carbazole-11, 12-diylbis (propan-1, 3-diyl)) bisphosphonic acid (A-7), (5, 6-difluoroindolo [2,3-a ] carbazole-11, 12-diylbis (butan-1, 4-diyl)) bisphosphonic acid (A-8).
The self-assembled monolayer hole transport material can be synthesized by the following two methods:
the method comprises the following steps: for R 2 The specific synthesis steps of the compound A with the general formula of hydrogen are as follows:
step 1:
the 4-substituted phenylhydrazine hydrochloride (the general formula compound I) and 1, 2-cyclohexanedione undergo Fischer cyclization reaction in glacial acetic acid to generate the general formula compound II; the molar ratio of the compound I with the general formula to the 1, 2-cyclohexanedione is 2.5-2.7:1, the reaction temperature is the reflux temperature of acetic acid, and the reaction time is controlled to be 18-24 h.
Step 2:
nucleophilic substitution reaction is carried out on the general formula compound II and 3-bromopropyl diethyl phosphonate or 4-bromopropyl diethyl phosphonate under the condition of taking NaH as a base to generate a general formula compound III; the mol ratio of the compound II with the general formula, the diethyl 3-bromopropyl phosphonate or the diethyl 4-bromobutyl phosphonate to the NaH is 1:2.2-2.7:2.5-3.0, the reaction temperature is room temperature, and the reaction time is controlled to be 10-12 h.
Step 3:
hydrolyzing the compound III with trimethyl bromosilane to obtain a compound A; the molar ratio of the compound III in the general formula to the trimethyl bromosilane is 1:10, the reaction temperature is room temperature, and the reaction time is controlled to be 10-12 h.
Method II: for R 2 The specific synthesis steps of the compound A with the general formula which is not hydrogen are as follows:
step 1:
carrying out Suzuki coupling reaction on the 5-substituted-2-nitrobenzoic acid (the general formula compound IV) and the general formula compound V in a palladium catalytic system to generate a general formula compound VI; in the general formula compound V, the substituent X can be bromine, iodine or trifluoro methanesulfonate, the molar ratio of the general formula compound VI to V is 2.5:1, and the palladium catalytic system is Pd 2 (dba) 3 /X-PhOS/K 2 CO 3 THF (beta), wherein the reaction temperature is 60-70 ℃ and the reaction time is controlled to be 12-24 h;
step 2:
under the action of triphenylphosphine, carrying out Cadougan ring closure reaction on the compound VI of the general formula to generate a compound VII of the general formula; the mol ratio of the compound VI shown in the general formula to triphenylphosphine is 1:4.5-5, the reaction temperature is 150-180 ℃, and the reaction time is controlled to be 10-12 h.
Step 3:
nucleophilic substitution reaction is carried out on the general formula compound VII and 3-bromopropyl diethyl phosphonate or 4-bromopropyl diethyl phosphonate under the condition of taking sodium hydride as a base, so as to generate the general formula compound VIII; the mol ratio of the compound VII of the general formula, the diethyl 3-bromopropyl phosphonate or the diethyl 4-bromobutyl phosphonate to the NaH is 1:2.2-2.7:2.5-3.0, the reaction temperature is room temperature, and the reaction time is controlled to be 10-12 h.
Step 4:
hydrolyzing the compound VIII with trimethyl bromosilane to obtain a compound A; the mol ratio of the compound VIII in the general formula to the trimethyl bromosilane is 1:10, the reaction temperature is room temperature, and the reaction time is controlled between 10 and 12 and h.
The self-assembled monolayer material shown in the general formula A can be used as a hole transport material for replacing PTAA to be applied to an inversion perovskite solar cell, and is beneficial to improving the efficiency of inversion PSCs.
The self-assembled monolayer material shown in the general formula A can also be used as a hole transport material for replacing PEDOT: PSS to be applied to a positive organic solar cell, and is beneficial to improving the efficiency and stability of positive OSCs.
The self-assembled monolayer material with the general formula A provided by the invention can also be used for modifying inorganic NiO x The hole transport material is applied to the inversion perovskite solar cell, and is beneficial to improving the efficiency of the inversion PSCs.
Advantages and beneficial effects of the invention
The self-assembled monolayer hole transport material containing the bisphosphonic acid terminal group provided by the invention has the advantages that the bisphosphonic acid terminal anchoring group can be firmly self-assembled with the surface of the substrate in a chemical bonding mode, so that the self-assembled monolayer hole transport material has good coverage rate; meanwhile, the rigid conjugated large-plane condensed ring core structure ensures the hole transmission performance of the material; by changing the substituent group or alkyl chain length of the condensed ring core, the properties of energy level, stacking mode, solubility, interface passivation and the like of molecules can be flexibly regulated and controlled, and the photovoltaic performance of the material is further improved. Owing to the self-assembled monolayer characteristic, when the self-assembled monolayer is used as a hole transport material, the self-assembled monolayer is very low in use concentration, can effectively reduce the preparation cost of the device, and is suitable for industrial application of organic solar cells or perovskite solar cells. When the synthesized material is directly used as a hole transport layer for the hole transport layer of an inversion perovskite solar cell, an open circuit voltage of more than 1.14V and a photoelectric conversion efficiency of more than 22% can be obtainedThe method comprises the steps of carrying out a first treatment on the surface of the When the polymer is directly used for a positive organic solar cell, the polymer can obtain more than 27mA cm -2 Short circuit current density of (2)>Photoelectric conversion efficiency of 19%; in addition, as NiO x Application of the modification layer material in the inversion perovskite solar cell can obtain open circuit voltage of more than 1.17V and>the photoelectric conversion efficiency of 22% is expected to help the industrialization of the two types of solar cells.
Drawings
FIG. 1 is a molecular structural general formula of a self-assembled monolayer material prepared by the invention;
FIG. 2 is a schematic diagram of a perovskite solar cell prepared according to the present invention with a self-assembled monolayer as a hole transport layer;
FIG. 3 is a schematic diagram of an organic solar cell prepared according to the present invention using a self-assembled monolayer as a hole transport layer;
FIG. 4 shows a self-assembled monolayer of NiO prepared according to the present invention x Schematic of perovskite solar cell of the modification layer;
FIG. 5 is a J-V plot of self-assembled monolayer materials A-1-A-8 (a-h) and commercial polymer PTAA (i) prepared according to the present invention as hole transport materials for perovskite solar cells;
FIG. 6 is a J-V plot of self-assembled monolayer materials A-1 to A-8 (a-h) and commercial polymer PEDOT: PSS (i) prepared according to the present invention as hole transport materials for organic solar cells;
FIG. 7 shows the self-assembled monolayer materials A-1 to A-8 modified NiO prepared according to the present invention x (a-h) and pure NiO x (i) J-V graph for perovskite solar cells as hole transport material.
Detailed Description
The present invention will be further described with reference to the following examples, which should not be construed as limiting the scope of the invention, in order to better understand the essential characteristics of the invention. It is also specifically noted herein that the specific experimental methods and apparatus referred to in the examples are conventional methods or carried out under the conditions recommended by the manufacturer's instructions unless otherwise specified, and that the reagents referred to are commercially available without otherwise specified.
Example 1
The preparation method of the compound A-1 comprises the following steps:
step 1: to a 250mL two-necked round bottom flask was added phenylhydrazine hydrochloride (I-1, 3.91g,27.0 mmol) and 1, 2-cyclohexanedione (1.12 g,10.0 mmol), after nitrogen substitution, 80mL glacial acetic acid (AcOH) was added, and after addition the system was warmed to reflux for 20h and monitored by Thin Layer Chromatography (TLC). After the reaction, the system was cooled to room temperature and concentrated in vacuo. The residue was dispersed in 50mL of water, extracted with ethyl acetate (50 ml×3), the organic phases were combined, washed with brine (30 mL), dried over anhydrous sodium sulfate, filtered, the filtrate concentrated under reduced pressure, separated by column chromatography, eluted with petroleum ether/ethyl acetate (v/v=10/1), and desolventized to give 1.61g of a white solid as compound II-1 in 63% yield.
Step 2: to a 50mL Shi Laike bottle was added compound II-1 (0.77 g,3.0 mmol), sodium hydride (60%, 360mg,9.0 mmol), 15mL of N, N-Dimethylformamide (DMF) was added after nitrogen substitution, and after stirring at room temperature for 20min, 3-bromopropylphosphonic acid diethyl ester (1.94 g,7.5 mmol) was slowly added dropwise thereto. After the dropping, the system was reacted at room temperature for 12 hours. After completion of the reaction, 50mL of water was added to the system, and the mixture was quenched with ethyl acetate (20 mL. Times.3), and the organic phases were combined, washed with water (20 mL) and brine (20 mL), respectively, and the organic layer was dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, purified by column chromatography, eluted with methylene chloride/methanol (v/v=20/1), and desolventized to give 1.63g of a pale yellow viscous liquid as compound III-1 in 89% yield.
Step 3: to a 100mL two-necked round bottom flask was added compound III-1 (1.23 g,2.0 mmol), after which 20mL of Dichloromethane (DCM) was added after nitrogen was replaced, followed by trimethylbromosilane (TMSBr, 3.1g,20.0 mmol) and reacted at room temperature for 12h. The reaction system was concentrated under reduced pressure, and then dissolved in 20mL of methanol, to which 20mL of water was added with stirring, to precipitate a product.Filtration and recrystallization of the filter cake from methanol/water (v/v=1/2) gave 721mg of white solid as compound a-1 in 72% yield. Nuclear magnetic resonance hydrogen spectrum [ ] 1 H NMR) data are shown in table 1.
Example 2
The preparation method of the compound A-2 comprises the following steps:
step 1: to a 250mL two-necked round bottom flask was added 4-fluorobenzenehydrazine hydrochloride (I-2, 4.39g,27.0 mmol) and 1, 2-cyclohexanedione (1.12 g,10.0 mmol), after nitrogen substitution 80mL AcOH was added and after the addition was complete the system was warmed to reflux for 20h and monitored by TLC. After the reaction, the system was cooled to room temperature and concentrated in vacuo. The residue was dispersed in 50mL of water, extracted with ethyl acetate (50 ml×3), the organic phases were combined, washed with brine (30 mL), dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, separated by column chromatography, eluted with petroleum ether/ethyl acetate (v/v=10/1), and desolventized to give 1.52g of a white solid as compound II-2 in 52% yield.
Step 2: to a 50mL Shi Laike bottle was added compound II-2 (0.66 g,2.3 mmol), sodium hydride (60%, 276mg,6.9 mmol), after nitrogen substitution, 10mL DMF was added, and after stirring at room temperature for 20min, diethyl 3-bromopropylphosphonate (1.46 g,5.7 mmol) was slowly added dropwise thereto. After the dropping, the system was reacted at room temperature for 12 hours. After completion of the reaction, 50mL of water was added to the system, and the mixture was quenched with ethyl acetate (20 mL. Times.3), and the organic phases were combined, washed with water (20 mL) and brine (20 mL), respectively, and the organic layer was dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, purified by column chromatography, eluted with methylene chloride/methanol (v/v=20/1), and desolventized to give 1.26g of a pale yellow viscous liquid as compound III-2 in 86% yield.
Step 3: to a 100mL two-necked round bottom flask was added compound III-2 (1.22 g,1.9 mmol), after nitrogen substitution, 20mL DCM was added thereto, followed by TMSBr (2.9 g,19.0 mmol) and the reaction was carried out at room temperature for 12h. The reaction system was concentrated under reduced pressure, and then dissolved in 20mL of methanol, and stirred to itTo this was added 20mL of water to precipitate the product. After filtration, the filter cake was recrystallized from methanol/water (v/v=1/2) to give 648mg of a white solid as compound a-2 in 64% yield. 1 The H NMR data are shown in Table 1.
Example 3
The preparation method of the compound A-3 comprises the following steps:
step 1: to a 250mL two-necked round bottom flask was added 4-chlorophenylhydrazine hydrochloride (I-3, 4.83g,27.0 mmol) and 1, 2-cyclohexanedione (1.12 g,10.0 mmol), after nitrogen substitution, 80mL AcOH was added, and after the addition, the system was warmed to 120℃and refluxed for 24 hours and monitored by TLC. After the reaction, the system was cooled to room temperature and concentrated in vacuo. The residue was dispersed in 80mL of water, extracted with ethyl acetate (100 ml×3), the organic phases were combined, washed with brine (50 mL), dried over anhydrous sodium sulfate and filtered, the filtrate was desolventized under reduced pressure, and the solid was recrystallized from petroleum ether/ethyl acetate (100 mL, v/v=20/1) to give 1.91g of a white solid as compound II-3 in 59% yield.
Step 2: to a 50mL Shi Laike bottle was added compound II-3 (0.65 g,2.0 mmol), sodium hydride (60%, 240mg,6.0 mmol), after replacing nitrogen, 10mL DMF was added, and after stirring at room temperature for 20min, diethyl 4-bromobutylphosphonate (1.36 g,5.0 mmol) was slowly added dropwise thereto. After the dropping, the system was reacted at room temperature for 12 hours. After completion of the reaction, 50mL of water was added to the system, and the mixture was quenched with ethyl acetate (20 mL. Times.3), and the organic phases were combined, washed with water (20 mL) and brine (20 mL), respectively, and the organic layer was dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, purified by column chromatography, eluted with methylene chloride/methanol (v/v=20/1), and desolventized to give 1.19g of a pale yellow viscous liquid as compound III-3 in 84% yield.
Step 3: to a 100mL two-necked round bottom flask was added compound III-3 (1.06 g,1.5 mmol), after nitrogen substitution, 20mL DCM was added thereto, followed by TMSBr (2.3 g,15.0 mmol) and the reaction was carried out at room temperature for 10h. The reaction system was concentrated under reduced pressure and then dissolved in 20mL of methanol with stirringTo this was added 20mL of water to precipitate the product. Filtration and recrystallization of the filter cake from methanol/water (v/v=1/2) gave 644mg of white solid as compound a-3 in 72% yield. 1 The H NMR data are shown in Table 1.
Example 4
The preparation method of the compounds A-4 and A-5 comprises the following steps:
step 1: to a 250mL two-necked round bottom flask was added 4-bromophenylhydrazine hydrochloride (I-4, 8.94g,39.0 mmol) and 1, 2-cyclohexanedione (1.68 g,15.0 mmol), after nitrogen substitution 100mL AcOH was added, and after the addition, the system was warmed to 120℃and refluxed for 24h and monitored by TLC. After the reaction, the system was cooled to room temperature and concentrated in vacuo. The residue was dispersed in 80mL of water, extracted with ethyl acetate (100 ml×3), the organic phases were combined, washed with brine (50 mL), dried over anhydrous sodium sulfate and filtered, the filtrate was desolventized under reduced pressure, and the solid was recrystallized from petroleum ether/ethyl acetate (200 mL, v/v=20/1) to give 4.9g of a white solid as compound II-4 in 79% yield.
Step 2: to a 50mL Shi Laike bottle was added compound II-4 (1.03 g,2.5 mmol), sodium hydride (60%, 300mg,7.5 mmol), after nitrogen substitution, 10mL DMF was added, and after stirring at room temperature for 20min, 3-bromopropylphosphonic acid diethyl ester or 4-bromobutylphosphonic acid diethyl ester (6.3 mmol) was slowly added dropwise thereto. After the dropping, the system was reacted at room temperature for 12 hours. After completion of the reaction, 50mL of water was added to the system, and the mixture was quenched with ethyl acetate (20 mL. Times.3), the organic phases were combined, washed with water (20 mL) and brine (20 mL), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure, purified by column chromatography, eluted with methylene chloride/methanol (v/v=20/1), and desolventized to give compound III-4 (3.39 g, 88%) and compound III-5 (3.39 g, 88%)
Step 3: to a 100mL two-necked round bottom flask was added compound III-4 or III-5 (1.5 mmol), to which 20mL DCM was added after nitrogen substitution, followed by TMSBr (2.3 g,15.0 mmol) and reacted at room temperature for 10h. Concentrating the reaction system under reduced pressure and dissolvingSolution in 20mL of methanol, 20mL of water was added thereto with stirring, and the product was precipitated. After filtration, the cake was recrystallized from methanol/water (v/v=1/2) to give compound a-4 (pale yellow solid, 720mg, yield 73%) or compound a-5 (pale yellow solid, 720mg, yield 73%). 1 The H NMR data are shown in Table 1.
Example 5
The preparation method of the compound A-6 comprises the following steps:
step 1: to a 250mL two-necked round bottom flask was added 4-methoxyphenylhydrazine hydrochloride (I-5, 8.94g,39.0 mmol) and 1, 2-cyclohexanedione (1.68 g,15.0 mmol), after nitrogen substitution 100mL AcOH was added, and after the addition, the system was warmed to 120℃and refluxed for 24h and monitored by TLC. After the reaction, the system was cooled to room temperature and concentrated in vacuo. The residue was dispersed in 80mL of water, extracted with ethyl acetate (100 ml×3), the organic phases were combined, washed with brine (50 mL), dried over anhydrous sodium sulfate and filtered, the filtrate was desolventized under reduced pressure, and the solid was recrystallized from petroleum ether/ethyl acetate (200 mL, v/v=20/1) to give 4.9g of a white solid as compound II-5 in 79% yield.
Step 2: to a 50mL Shi Laike bottle was added compound II-5 (1.03 g,2.5 mmol), sodium hydride (60%, 300mg,7.5 mmol), after nitrogen substitution, 10mL DMF was added, and after stirring at room temperature for 20min, 3-bromopropylphosphonic acid diethyl ester or 4-bromobutylphosphonic acid diethyl ester (6.3 mmol) was slowly added dropwise thereto. After the dropping, the system was reacted at room temperature for 12 hours. After completion of the reaction, 50mL of water was added to the system, and the mixture was quenched with ethyl acetate (20 mL. Times.3), the organic phases were combined, washed with water (20 mL) and brine (20 mL), respectively, the organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure, purified by column chromatography, eluted with methylene chloride/methanol (v/v=20/1), and desolventized to give compound III-6 (3.39 g, 88%)
Step 3: into a 100mL two-necked round bottom flask was charged compound III-4 or III-5 (1.5 mmol), after nitrogen substitution 20mL DCM was added thereto followed by TMSBr (2.3 g,15.0 mmol) and the chamberThe reaction was carried out at a temperature for 10 hours. The reaction system was concentrated under reduced pressure, and then dissolved in 20mL of methanol, to which 20mL of water was added with stirring, to precipitate a product. Filtering, and recrystallizing the filter cake with methanol/water (v/v=1/2) to obtain the compound A-6. 1 The H NMR data are shown in Table 1.
Example 6
The preparation method of the compounds A-7 and A-8 comprises the following steps:
step 1: into a 250mL two-necked round bottom flask was charged 2-nitrobenzoic acid (IV-1, 4.17g,25.0 mmol), 1, 4-dibromo-2, 3-difluorobenzene (V-1, 2.72g,10.0 mmol), pd 2 (dba) 3 (183mg, 0.2 mmol), X-PhOS (191 mg,0.4 mmol) and anhydrous potassium carbonate (4.25 g,30.0 mmol), 50mL Tetrahydrofuran (THF) was added after nitrogen substitution, and the system was warmed to 70℃after the addition to react for 18h and monitored by TLC. After the reaction was completed, the system was cooled to room temperature, and the solution was filtered through celite. The filtrate was concentrated in vacuo and separated by column chromatography eluting with petroleum ether/dichloromethane (v/v=3/1) to give 2.56g of a white solid as compound VI-1 in 72% yield.
Step 2: to a 100mL two-necked round bottom flask were added compound VI-1 (2.37 g,6.5 mmol) and triphenylphosphine (7.66 g,29.3 mmol), after nitrogen substitution, 30mL o-Dichlorobenzene (DCB) was added, and after the addition, the system was warmed to 180℃and refluxed for 12 hours and monitored by Thin Layer Chromatography (TLC). After the reaction was completed, the system was cooled to room temperature. The solution was concentrated in vacuo and separated by column chromatography eluting with petroleum ether/ethyl acetate (v/v=5/1) to give 1.39g of a white solid as compound VII-1 in 73% yield.
Step 3: to a 50mL Shi Laike bottle was added compound VII-1 (730 mg,2.5 mmol), sodium hydride (60%, 300mg,7.5 mmol), after displacing nitrogen, 10mL DMF was added, and after stirring at room temperature for 20min, 3-bromopropyl phosphonic acid diethyl ester or 4-bromobutyl phosphonic acid diethyl ester (6.3 mmol) was slowly added dropwise thereto. After the dropping, the system was reacted at room temperature for 10 hours. After completion of the reaction, 50mL of water was added to the system, and extracted with ethyl acetate (20 ml×3), and the organic phases were combined, washed with water (20 ml×3) and brine (20 mL), respectively, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure, purified by column chromatography, eluting with methylene chloride/methanol (v/v=20/1) to give compound VIII-1 (1.44 g, yield 89%, as pale yellow viscous liquid) or VIII-2 (1.54 g, yield 91%, as pale yellow viscous liquid).
Step 4: to a 100mL two-necked round bottom flask was added compound VIII-1 or VIII-2 (2.0 mmol), to which 20mL DCM was added after nitrogen substitution, followed by TMSBr (2.7 mL,20.0 mmol) and the reaction was carried out at room temperature for 12h. The reaction system was concentrated under reduced pressure, and then dissolved in 10mL of methanol, to which 20mL of water was added with stirring, to precipitate a product. After filtration, the filter cake was recrystallized from methanol/water (v/v=1/2) to give compound a-7 (750 mg, yield 64% as white solid) or a-8 (816 mg, yield 69% as white solid). 1 The H NMR data are shown in Table 1.
Photovoltaic device preparation and performance test application examples
Example 8
Device preparation and photovoltaic performance test as self-assembled single-molecule hole transport layer for inversion PSCs:
perovskite solar cells were prepared using as hole transport layers the synthesized self-assembled monolayer materials (SAMs) A-1 to A-8, as shown in FIG. 2, having the structure: glass/ITO/SAM/perovskite/PCBM/BCP/Ag. And sequentially ultrasonically cleaning the ITO conductive glass with detergent, deionized water, acetone and isopropanol for 30min. After nitrogen is dried, the ITO glass is cleaned by adopting plasma for 15min. SAM A-1 to A-8 are respectively used as hole transport layers, 0.1 to 0.25mg/mL of methanol solution is spin-coated on ITO glass, the rotating speed is 3000 to 4000rpm, the heat annealing treatment is carried out for 10 to 15 minutes at 100 ℃, and after cooling, the redundant SAM molecules on the surface are washed by methanol. Subsequently, 1.5M Cs were removed 0.06 FA 0.80 MA 0.14 PbI 3 The perovskite solution is spin-coated on the surface of SAM, and is heat annealed at 110 ℃ for 20min. After cooling, 20mg/ml PCBM and 0.6mg/ml BCP were spin-coated on the perovskite film surface at 1200rpm and 1000rpm, respectively. Finally, vacuum evaporating a layer of 100nm Ag as an electrode, thereby completing the manufacture of the perovskite solar cell deviceThe effective area of the device is 10mm 2 . The intensity of the light source was measured to be AM 1.5G,100mW cm using a xenon lamp solar simulator -2 Open circuit voltage (V) for manufacturing battery device OC ) Density of short-circuit current (J) SC ) The Fill Factor (FF) and the Photoelectric Conversion Efficiency (PCE) were tested. The current-voltage curve test results are shown in fig. 5 (a-h), and the photovoltaic performance parameters are shown in table 2.
Example 9
Device preparation and photovoltaic performance test of the self-assembled single-molecule hole transport layer for positive OSCs:
the organic solar cell is prepared by taking the synthesized self-assembled monolayer materials (SAM) A-1 to A-8 as a hole transport layer, and has the structure of glass/ITO/SAM/organic bulk heterojunction/PNDIT-F3N/Ag as shown in figure 3. And sequentially ultrasonically cleaning the ITO conductive glass by using a cleaning agent, deionized water, acetone and isopropanol for 30min for standby. Ozone treatment is carried out on the cleaned substrate for 15min before trial; SAM A-1 to A-8 are respectively used as hole transport layers, ethanol solution of 0.3 to 0.7mg/mL is spin-coated on ITO, the rotating speed is 2000 to 3000rpm, the heat annealing treatment is carried out for 10 minutes at 80 ℃, and then the solution diluted to half of the original concentration is used for spin-coating once again at the same rotating speed, so that the monomolecular HTL is obtained. Next, a BHJ active layer is prepared, wherein the solution consists of a polymer donor PM6, a small molecule acceptor L8-BO, a chloroform solvent, and the acceptor mass ratio is 1:1.2, the total concentration is 15.4mg/mL,0.25% DIO is used as an additive, 20s at 3000rpm, and annealing is performed for 10min at 100 ℃ after spin coating; after cooling, an electron transport layer PNDIT-F3N, methanol solvent, was spin-coated on its upper surface at a concentration of 1mg/mL,3000rpm, 20s. Finally, evaporating a layer under high vacuumThe Ag of the (B) is used as an electrode, thereby completing the preparation of the organic solar cell device, and the effective area of the device is 4mm 2 . The intensity of the light source was measured to be AM 1.5G at 100mW cm using a solar simulator -2 V for preparing battery device OC 、J SC Tests were performed on FF and PCE. The current-voltage curve test results are shown in fig. 6 (a-h), and the photovoltaic performance parameters are shown in table 2.
Example 10
Device preparation and photovoltaic performance test of inverse PSCs as nickel oxide modification layer:
the synthesized self-assembled monolayer materials (SAM) A-1 to A-8 are used as NiO x The perovskite solar cell is prepared by the modification layer of (1) and has the structure of glass/ITO/NiO as shown in figure 4 x SAM/perovskite/PCBM/BCP/Ag. And sequentially ultrasonically cleaning the ITO conductive glass with detergent, deionized water, acetone and isopropanol for 30min. After nitrogen is dried, the ITO glass is cleaned by adopting plasma for 15min. 20mg/ml NiO x The aqueous dispersion is spin-coated on ITO at a rotation speed of 5000rpm, and is subjected to thermal annealing treatment at 150 ℃ for 15-20 min, SAM A-1-A-8 are respectively used as NiO x Is spin-coated on NiO with 0.1-0.25 mg/mL of methanol solution x And (3) performing thermal annealing treatment at 80 ℃ for 10min at the rotating speed of 2500-3000 rpm. Next, 1.5M Cs was added 0.06 FA 0.80 MA 0.14 PbI 3 The perovskite solution is spin-coated on the surface of SAM, and is heat annealed at 110 ℃ for 15-20 min. After cooling, 20mg/mL of PCBM and 0.6mg/mL of BCP were spin coated on the perovskite film surface at 1200rpm and 1000rpm, respectively. Finally, vacuum evaporating a layer of 100nm Ag as an electrode, thereby completing the preparation of the perovskite solar cell device, wherein the effective area of the device is 10mm 2 . The intensity of the light source was measured to be AM 1.5G,100mW cm using a xenon lamp solar simulator -2 V for preparing battery device OC 、J SC Tests were performed on FF and PCE. The current-voltage curve test results are shown in fig. 7 (a-h), and the photovoltaic performance parameters are shown in table 3.
Comparative example 1
The perovskite solar cell is prepared by taking PTAA as a hole transport layer, and has the structure as follows: glass/ITO/PTAA/perovskite/PCBM/BCP/Ag. And sequentially ultrasonically cleaning the ITO conductive glass with detergent, deionized water, acetone and isopropanol for 30min. After nitrogen is dried, the ITO glass is cleaned by adopting plasma for 15min. PTAA is spin-coated on ITO glass at 3000-4000 rpm in methanol solution of 0.1-0.25 mg/mL, heat annealed at 100 ℃ for 10-15 min, cooled and placed in a glove box for standby. Subsequently, 1.5M Cs were removed 0.06 FA 0.80 MA 0.14 PbI 3 The perovskite solution is spin-coated on the PTAA surface and is subjected to thermal annealing treatment at 110 ℃ for 20min. After cooling, 20mg/ml PCBM and 0.6mg/ml BCP were spin-coated on the perovskite film surface at 1200rpm and 1000rpm, respectively. Finally, vacuum evaporating a layer of 100nm Ag as an electrode, thereby completing the preparation of the perovskite solar cell device, wherein the effective area of the device is 10mm 2 . The intensity of the light source was measured to be AM 1.5G,100mW cm using a xenon lamp solar simulator -2 V for preparing battery device OC 、J SC Tests were performed on FF and PCE. The current-voltage curve test results are shown in fig. 5 (i), and the photovoltaic performance parameters are shown in table 2.
Comparative example 2
The organic solar cell is prepared by taking PEDOT and PSS as hole transport layers, and has the structure as follows: glass/ITO/PEDOT PSS/organic active layer/PNDIT-F3N/Ag. And sequentially ultrasonically cleaning the ITO conductive glass by using a cleaning agent, deionized water, acetone and isopropanol for 30min for standby. Ozone treatment is carried out on the cleaned substrate for 15min before trial; commercial PEDOT-PSS aqueous solution is spin-coated on ITO at 4000rpm, and is subjected to thermal annealing at 160 ℃ for 15min, and placed in a glove box for standby. Next, a BHJ active layer was prepared, the solution composition was polymer donor PM6 and small molecule acceptor L8-BO, chloroform solvent, the acceptor mass ratio was 1:1.2, total concentration was 15.4mg/mL,0.25% DIO was used as additive, spin-coated at 3000rpm for 20s, followed by annealing at 100℃for 10min; after cooling, an electron transport layer PNDIT-F3N, methanol solvent, was spin-coated on its upper surface at a concentration of 1mg/mL,3000rpm, 20s. Finally, evaporating a layer under high vacuumThe Ag of the (B) is used as an electrode, thereby completing the preparation of the organic solar cell device, and the effective area of the device is 4mm 2 . The intensity of the light source was measured to be AM 1.5G at 100mW cm using a solar simulator -2 V for preparing battery device OC 、J SC Tests were performed on FF and PCE. The current-voltage curve test results are shown in fig. 6 (i), and the photovoltaic performance parameters are shown in table 2.
Comparative example 3
With NiO x Preparation of calcium for hole transport layer materialsThe titanium ore solar cell has the structure of glass/ITO/NiO x perovskite/PCBM/BCP/Ag. And sequentially ultrasonically cleaning the ITO conductive glass with detergent, deionized water, acetone and isopropanol for 30min. After nitrogen is dried, the ITO glass is cleaned by adopting plasma for 15min. 20mg/ml NiO x The aqueous dispersion is spin-coated on ITO at a rotation speed of 5000rpm, and is subjected to thermal annealing at 150 ℃ for 15-20 min. Next, 1.5M Cs was added 0.06 FA 0.80 MA 0.14 PbI 3 Spin coating perovskite solution to NiO x And carrying out heat annealing treatment at 110 ℃ on the surface for 20min. After cooling, 20mg/mL PCBM and 0.6mg/mL BCP were spin-coated on the perovskite film surface at 1200rpm and 1000rpm, respectively. Finally, vacuum evaporating a layer of 100nm Ag as an electrode, thereby completing the preparation of the perovskite solar cell device, wherein the effective area of the device is 10mm 2 . The intensity of the light source was measured to be AM 1.5G,100mW cm using a xenon lamp solar simulator -2 V for preparing battery device OC 、J SC Tests were performed on FF and PCE. The current-voltage curve test results are shown in fig. 7 (i), and the photovoltaic performance parameters are shown in table 2.
Table 1 shows the structures and partial structures of the compounds of the general formulae A-1 to A-8 1 H NMR data; table 2 shows the photovoltaic performance parameters of the inverted PSCs and the positive OSCs based on a portion of the compounds of the general formulae A-1 to A-8.
TABLE 1
TABLE 2
TABLE 3 Table 3
Claims (9)
1. A self-assembled monolayer hole transport material containing a bisphosphonic acid end group is characterized in that: has a structural formula shown in a general formula A:
wherein:
R 1 hydrogen, fluorine, chlorine, bromine, cyano, methyl, trifluoromethyl or methoxy;
R 2 is hydrogen, fluoro, cyano or a condensed substituted thiadiazole;
n is 3 or 4.
2. The self-assembled monolayer hole transporting material comprising bisphosphonic acid end groups of claim 1, characterized in that: the self-assembled monolayer hole transport material containing the bisphosphonic acid terminal group is specifically the following compounds: (indolo [2,3-a ] carbazole-11, 12-diylbis (prop-1, 3-diyl)) bisphosphonic acid (A-1), (3, 8-difluoroindolo [2,3-a ] carbazole-11, 12-diylbis (prop-1, 3-diyl)) bisphosphonic acid (A-2), (3, 8-dichloroindolo [2,3-a ] carbazole-11, 12-diylbis (but-1, 4-diyl)) bisphosphonic acid (A-3), (3, 8-dibromoindolo [2,3-a ] carbazole-11, 12-diylbis (prop-1, 3-diyl)) bisphosphonic acid (A-4) (3, 8-dibromoindolo [2,3-a ] carbazole-11, 12-diylbis (butan-1, 4-diyl)) bisphosphonic acid (a-5), (3, 8-dimethoxyindolo [2,3-a ] carbazole-11, 12-diylbis (butan-1, 4-diyl)) bisphosphonic acid (a-6), (5, 6-difluoroindolo [2,3-a ] carbazole-11, 12-diylbis (propan-1, 3-diyl)) bisphosphonic acid (a-7) and (5, 6-difluoroindolo [2,3-a ] carbazole-11, 12-diylbis (butan-1, 4-diyl)) bisphosphonic acid (a-8).
3. A method for preparing a self-assembled monolayer hole transport material comprising a bisphosphonic acid end group according to claim 1, characterized in that: can be synthesized by the following two methods:
the method comprises the following steps: for R 2 The specific synthesis steps of the compound A with the general formula of hydrogen are as follows:
step 1:
the 4-substituted phenylhydrazine hydrochloride shown in the general formula compound I and 1, 2-cyclohexanedione undergo Fischer cyclization in glacial acetic acid to generate a general formula compound II; the molar ratio of the compound I with the general formula to the 1, 2-cyclohexanedione is 2.5-2.7:1, the reaction temperature is the reflux temperature of acetic acid, and the reaction time is controlled to be 18-24 hours;
step 2:
nucleophilic substitution reaction is carried out on the general formula compound II and 3-bromopropyl diethyl phosphonate or 4-bromopropyl diethyl phosphonate under the condition of taking NaH as a base to generate a general formula compound III; the mol ratio of the compound II with the general formula, the diethyl 3-bromopropyl phosphonate or the diethyl 4-bromobutyl phosphonate to the NaH is 1:2.2-2.5:2.7-3.0, the reaction temperature is room temperature, and the reaction time is controlled to be 10-12 h;
step 3:
hydrolyzing the compound III with trimethyl bromosilane to obtain a compound A; the molar ratio of the compound III in the general formula to the trimethyl bromosilane is 1:10, the reaction temperature is room temperature, and the reaction time is controlled to be 10-12 h;
the second method is as follows: for R 2 The specific synthesis steps of the compound A with the general formula which is not hydrogen are as follows:
step 1:
the 5-substituted-2-nitrobenzoic acid shown in the general formula compound IV and the general formula compound V are shown in the specificationGenerating a Suzuki coupling reaction in a palladium catalytic system to generate a general formula compound VI; in the general formula compound V, the substituent X can be bromine, iodine or trifluoro methanesulfonate, the molar ratio of the general formula compound VI to V is 2.5:1, and the palladium catalytic system is Pd 2 (dba) 3 /X-PhOS/K 2 CO 3 THF (beta), wherein the reaction temperature is 60-70 ℃ and the reaction time is controlled to be 12-24 h;
step 2:
under the action of triphenylphosphine, carrying out Cadougan ring closure reaction on the compound VI of the general formula to generate a compound VII of the general formula; the mol ratio of the compound VI with the general formula to triphenylphosphine is 1:4.5-5, the reaction temperature is 150-180 ℃, and the reaction time is controlled to be 10-12 h;
step 3:
nucleophilic substitution reaction is carried out on the general formula compound VII and 3-bromopropyl diethyl phosphonate or 4-bromopropyl diethyl phosphonate under the condition of taking sodium hydride as a base, so as to generate the general formula compound VIII; the mol ratio of the compound VII of the general formula, the diethyl 3-bromopropyl phosphonate or the diethyl 4-bromobutyl phosphonate to the NaH is 1:2.2-2.7:2.5-3.0, the reaction temperature is room temperature, and the reaction time is controlled to be 10-12 h;
step 4:
hydrolyzing the compound VIII with trimethyl bromosilane to obtain a compound A; the mol ratio of the compound VIII in the general formula to the trimethyl bromosilane is 1:10, the reaction temperature is room temperature, and the reaction time is controlled to be 10-12 h.
4. Use of a self-assembled monolayer hole-transporting material comprising bisphosphonic acid end groups according to claim 1, characterized in that: the self-assembled monolayer hole transport material containing the bisphosphonic acid end group is applied to an inversion perovskite solar cell.
5. The use of a self-assembled monolayer hole-transporting material according to claim 4, wherein: the perovskite solar cell comprises the following structures from bottom to top: glass/ITO/SAM/perovskite active layer/PCBM/BCP/Ag, wherein the SAM is self-assembled monolayer hole transport material containing a bisphosphonic acid terminal group.
6. Use of a self-assembled monolayer hole-transporting material comprising bisphosphonic acid end groups according to claim 1, characterized in that: the self-assembled monolayer hole transport material containing the bisphosphonic acid end group is applied to a positive organic solar cell.
7. The use of a self-assembled monolayer hole-transporting material according to claim 6, wherein: the structure of the organic solar cell is as follows from bottom to top: glass/ITO/SAM/organic active layer/PNDIT-F3N/Ag, wherein the SAM is self-assembled monolayer hole transport material containing a bisphosphonic acid terminal group.
8. Use of a self-assembled monolayer hole-transporting material comprising bisphosphonic acid end groups according to claim 1, characterized in that: the self-assembled monolayer hole transport material containing the bisphosphonic acid terminal group is used as NiO x The modification layer material is applied to an inversion perovskite solar cell.
9. Use of a self-assembled monolayer hole-transporting material according to claim 8, wherein: the perovskite solar cell comprises the following structures from bottom to top: glass/ITO/NiO x SAM/perovskite/PCBM/BCP/Ag, the SAM is self-containing bisphosphonic acid terminal groupA monolayer hole transport material is assembled.
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