CN112250677A - Organic small molecule hole transport material based on spiro [ fluorene-9, 9' -xanthene ], preparation method and application thereof - Google Patents
Organic small molecule hole transport material based on spiro [ fluorene-9, 9' -xanthene ], preparation method and application thereof Download PDFInfo
- Publication number
- CN112250677A CN112250677A CN202011108261.7A CN202011108261A CN112250677A CN 112250677 A CN112250677 A CN 112250677A CN 202011108261 A CN202011108261 A CN 202011108261A CN 112250677 A CN112250677 A CN 112250677A
- Authority
- CN
- China
- Prior art keywords
- spiro
- hole transport
- xanthene
- fluorene
- transport material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 65
- 230000005525 hole transport Effects 0.000 title claims abstract description 46
- QQNLHOMPVNTETJ-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 QQNLHOMPVNTETJ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000003384 small molecules Chemical class 0.000 title claims description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000012043 crude product Substances 0.000 claims description 19
- 239000012046 mixed solvent Substances 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- WKLIXKSNYFAGEH-UHFFFAOYSA-N 2,2',7,7'-tetrabromospiro[fluorene-9,9'-xanthene] Chemical compound Brc1ccc2-c3ccc(Br)cc3C3(c2c1)c1cc(Br)ccc1Oc1ccc(Br)cc31 WKLIXKSNYFAGEH-UHFFFAOYSA-N 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 12
- 238000010898 silica gel chromatography Methods 0.000 claims description 12
- 239000012467 final product Substances 0.000 claims description 6
- 125000003003 spiro group Chemical group 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- -1 5- (5-hexylthiophen-2-yl) thiophen-2-yl Chemical group 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QZVHYFUVMQIGGM-UHFFFAOYSA-N 2-Hexylthiophene Chemical compound CCCCCCC1=CC=CS1 QZVHYFUVMQIGGM-UHFFFAOYSA-N 0.000 description 4
- NUONHINJVGHSCL-UHFFFAOYSA-N 2-hexyl-5-thiophen-2-ylthiophene Chemical compound S1C(CCCCCC)=CC=C1C1=CC=CS1 NUONHINJVGHSCL-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 3
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 3
- CWGRCRZFJOXQFV-UHFFFAOYSA-N 2,7-dibromofluoren-9-one Chemical compound C1=C(Br)C=C2C(=O)C3=CC(Br)=CC=C3C2=C1 CWGRCRZFJOXQFV-UHFFFAOYSA-N 0.000 description 3
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 3
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 3
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- HQALDKFFRYFTKP-UHFFFAOYSA-N 2-[4-[4-(2-benzyl-1-benzothiophen-3-yl)phenyl]-2-bromo-6-(3-methoxyphenyl)phenoxy]acetic acid Chemical compound COC1=CC=CC(C=2C(=C(Br)C=C(C=2)C=2C=CC(=CC=2)C=2C3=CC=CC=C3SC=2CC=2C=CC=CC=2)OCC(O)=O)=C1 HQALDKFFRYFTKP-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 241000589970 Spirochaetales Species 0.000 description 1
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more 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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- 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
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a spiro [ fluorene-9, 9 '-xanthene ] based organic micromolecule hole transport material, a preparation method and application thereof, wherein the spiro [ fluorene-9, 9' -xanthene ] is taken as a core of the organic micromolecule hole transport material, so that the organic micromolecule hole transport material has a good amorphous state and excellent solubility; the side chain is added with thiophene groups with different numbers, and the material is endowed with more excellent physical and photoelectric properties through the characteristics of high electron density, excellent carrier transmission capability, controllable optical and electrochemical properties and the like; the modification of the terminal alkyl chain increases the solubility of the material, is favorable for the film-forming property of the material and is easier to process; meanwhile, the compound is synthesized by a simple synthetic route, and the raw materials are easy to obtain and the cost is low; the organic micromolecule hole transport material is applied to the all-inorganic perovskite solar cell, the cell efficiency is higher than that of the original cell, and the organic micromolecule hole transport material has practical significance for improving the efficiency of the all-inorganic perovskite solar cell.
Description
Technical Field
The invention relates to the technical field of solar cell materials, in particular to a spiro [ fluorene-9, 9' -xanthene ] based organic micromolecule hole transport material and a preparation method and application thereof.
Background
Since the perovskite solar cell is reported for the first time in 2009 by professor Tsutomu Miyasaka of university of tung shadow cross shore in japan, the research of the perovskite solar cell has made a major breakthrough through the improvement of materials and the optimization of device structure, and is the third generation solar cell which is closest to commercialization at present. In the perovskite solar cell structure, a hole transport material is of great importance and is one of the key factors influencing the cell performance. Among them, small molecule HTMS is widely used in high efficiency perovskite type solar cells due to its key role in charge carrier transport and charge recombination retardation. So far, amorphous organic spirochete-OMeTAD is the best choice for perovskite solar cells, a spirochete central unit and a large-volume diphenylamine substituted unit of the material endow a specific positive cross structure of spirochete-OMeTAD, and the structural characteristic weakens intermolecular accumulation and improves the solubility and film forming property of the material. However, the defects of poor crystallinity, environmental degradation, multiple synthesis methods, high cost, strong charge accumulation and the like still limit the application of the method.
For the above reasons, alternatives are widely used, such as spiro derivatives, triphenylamine, bridged triphenylamine, 3, 4-ethylenedioxythiophene, linear pi-conjugated systems, triptycene, tetraphenylethylene, triazine, etc., which are then all suitably decorated with diarylamine, triarylamine, or thiophene side groups, thereby achieving high efficiency, low cost, high stability perovskite solar cells. As the material with higher melting point and glass transition temperature is generally used for improving the thermal stability of the device, the spirofluorene material is still used in the invention because the spirofluorene material has a special rigid structure, a series of derivatives synthesized by the spirofluorene material have higher melting point and glass transition temperature, can inhibit the crystallization of molecules, has good film forming property and can improve the thermodynamic stability of the molecules. In the spirofluorene material, 9,9' -xanthene spirofluorene is connected with two parts of fluorene and xanthene through a central sp3 hybridized C atom, and can be modified by different organic groups at different positions, so that the molecular structure has the combination of electron-rich xanthene ring and fluorene, which can promote hole transmission capability, and the spirocycle can effectively construct a non-planar three-dimensional molecular conformation in the fields of molecular electrons and solid-state electrons. The steric hindrance effect can effectively inhibit the pi-pi stacking interaction between molecules, thereby improving the stability of the material and prolonging the service life of the device, and the highest occupied orbital (HOMO), the lowest unoccupied orbital (LUMO), the orbital distribution and the optical band gap of the molecules can be effectively changed by introducing electron donor and electron acceptor groups at different positions. Can improve the molecular weight and is beneficial to the improvement of the thermal stability of the material. Meanwhile, oligothiophene with high electron density and good hole mobility and alkyl chain with good solubility are used as side chains, so that the optical and electrochemical properties of the compound are easy to regulate and control. In addition, compared with the Spiro-OMeTAD, the material is simpler to synthesize, lower in manufacturing cost and higher in stability, so that the material has the potential of being an excellent hole transport material.
Disclosure of Invention
Aiming at the problem of low photoelectric conversion efficiency of all-inorganic perovskite in the prior art, the invention aims to provide an oligothiophene derivative organic micromolecule hole transport material with a spiro structure and good hydrophobicity and organic solubility, which is applied to a perovskite solar cell, has matched energy levels, can absorb red light, and can greatly improve the current density and the photoelectric conversion efficiency of the perovskite solar cell.
In order to achieve the purpose, the invention provides the following technical scheme:
a spiro [ fluorene-9, 9' -xanthene ] based organic small molecule hole transport material has a structural formula as follows:
the preparation method comprises the following steps: under the protection of nitrogen, 190mg,0.3mmol of compound 2,2',7,7' -tetrabromo spiro [ fluorene-9, 9' -xanthene]1.5mmol of 2-hexyl-5-tributyltin thiophene, 0.03mmol of Pd (PPh)3)4And 30mL of toluene are sequentially added into a 50mL dry double-neck bottle, the mixture is pumped and discharged for three times through a double-row pipe, the mixture is placed at the temperature of 110 ℃, the mixture is stirred and reacted for 48 hours in a dark place, the mixture is cooled to the room temperature, the crude product is purified through a silica gel column chromatography after a rotary evaporator is used for removing redundant mixed solvent, and normal hexane/dichloromethane (10/1, V/V) is used as an eluent, so that a light yellow transparent crystal compound, namely a final product, is obtained.
A spiro [ fluorene-9, 9' -xanthene ] based organic small molecule hole transport material has a structural formula as follows:
the preparation method comprises the following steps: under the protection of nitrogen, 190mg,0.3mmol of compound 2,2',7,7' -tetrabromo spiro [ fluorene-9, 9' -xanthene]1.5mmol of 5-hexyl-5 '-tributyltin-2, 2' -bithiophene, 0.03mmol of Pd (PPh)3)4And 30mL of toluene are sequentially added into a 50mL dry double-neck bottle, the mixture is pumped and discharged for three times through a double-row pipe, the mixture is placed at the temperature of 110 ℃, the mixture is stirred and reacted for 48 hours in a dark place, the mixture is cooled to the room temperature, the crude product is purified through a silica gel column chromatography after a rotary evaporator is used for removing redundant mixed solvent, and normal hexane/dichloromethane (10/1, V/V) is used as an eluent, so that a light yellow transparent crystal compound, namely a final product, is obtained.
A spiro [ fluorene-9, 9' -xanthene ] based organic small molecule hole transport material has a structural formula as follows:
the preparation method comprises the following steps: under the protection of nitrogen, 190mg,0.3mmol of compound 2,2',7,7' -tetrabromo spiro [ fluorene-9, 9' -xanthene]1.5mmol of the compound 2- (5- (5-hexylthiophen-2-yl) thiophen-2-yl) -5-tributylstannothiophene, 0.03mmol of Pd (PPh)3)4And 30mL of toluene are sequentially added into a 50mL dry double-neck bottle, pumped and drained three times by a double-row pipe and placed at the temperature of 110 DEG CStirring and reacting for 48 hours in the dark, cooling to room temperature, removing excessive mixed solvent from the crude product by a rotary evaporator, purifying the crude product by silica gel column chromatography, and taking n-hexane/dichloromethane (10/1, V/V) as eluent to obtain a light yellow transparent crystal compound, namely the final product.
The invention also provides application of the spiro [ fluorene-9, 9' -xanthene ] based organic small molecule hole transport material in preparation of perovskite solar cells.
The organic micromolecule hole transport material based on spiro [ fluorene-9, 9' -xanthene ] has the following beneficial effects:
1. the organic micromolecule hole transport material based on the benzothiophenes has a special molecular structure, uses benzodithiophene as a molecular core, and has a good photoelectric effect; a small amount of alkyl chain is introduced on the molecule, so that the solubility and the hydrophobicity of the organic solvent of the material can be improved, and the stability of the battery is improved; modifying by halogen atoms to obtain better carrier mobility; the energy level can be adjusted by introducing a group with conjugated property to widen a molecular conjugated system; the special molecular design can effectively adjust the crystallinity of the benzothiophene derivatives, so that the material has both solubility and hole transmission performance, and the photoelectric conversion efficiency and the current density of the device are improved; compared with the Spiro-OMeTAD, the material is simpler to synthesize, lower in manufacturing cost and higher in stability, so that the material has the potential of being an excellent hole transport material;
2. the benzothiophene derivative organic micromolecule hole transport material is applied to the all-inorganic perovskite solar cell, higher open-circuit voltage and short-circuit current of the device are shown, and better photoelectric conversion efficiency is obtained.
Drawings
FIG. 1 is a solid UV absorption spectrum of a hole transport material of the present invention;
FIG. 2 is a cyclic voltammetry test spectrum of a hole transport material of the present invention;
FIG. 3 is a graph of the relationship between current and voltage of the hole transport material of the present invention applied to an all-inorganic perovskite solar cell;
fig. 4 is a structural view of the hole transport material of the present invention applied to an all-inorganic perovskite solar cell.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
The performance test of the reaction product of the embodiment of the invention is carried out on the following instruments: testing the solid ultraviolet absorption spectrum on an Shimadzu UV-2600 type ultraviolet spectrometer, and spinning the product solution on quartz glass to prepare a sample; cyclic voltammetry was performed using a CHI660C electrochemical workstation under argon protection using a three-electrode system (platinum carbon electrode as the working electrode, platinum sheet electrode as the auxiliary electrode, silver chloride electrode as the reference electrode).
Example 1
Synthesis of spiro [ fluorene-9, 9' -xanthene ] based organic small molecule hole transport material SFX-THIO 1:
2,2',7,7' -tetrabromo spiro [ fluorene-9, 9' -xanthene ] (1)
4-bromophenol (17.3g,100mmol), 2, 7-dibromo-9-fluorenone (3.38g,10mmol) and methanesulfonic acid d ═ 1.48g/ml,2.6ml,3.84g,40mmol) were charged to a 250ml two-necked flask under nitrogen protection, purged with nitrogen three times using a double-vented tube, then heated and stirred at 150 ℃ for 24 hours, the reaction was cooled to room temperature, 100ml of a methanol solution was slowly added to the mixture, and after white crystals were precipitated, filtration was performed and washing with a large amount of methanol to obtain 1, 5.9g (yield 91%) of a white crystalline compound.
1H NMR(500MHZ,CDCl3)δ:8.00(d,2H),7.69(d,2H),7.48(d,2H),7.43(s,2H),7.30(d,2H),6.53(s,2H).13C NMR:151.49,137.21,135.20,134.42,133.31,131.14,130.60,122.53,120.29,116.70。
2-hexyl thiophene (2)
Under the protection of nitrogen, 8.4g of thiophene and 200mL of anhydrous tetrahydrofuran are added into a 500mL double-necked bottle, double-calandria is pumped and drained for three times, the bottle is placed at-78 ℃, 0.11mol of n-butyllithium is slowly added into a constant-pressure burette, then the bottle is slowly dripped into a reaction system, the reaction system is reacted for 30 minutes at low temperature and is reacted for 40 minutes at room temperature, the bottle is placed at-78 ℃, 0.11mol of 1-bromo-n-decane is added, the reaction is stirred overnight, 200mL of deionized water is added to stop the reaction, ether is extracted for three times, organic phases are combined, the organic phases are sequentially washed by saturated sodium chloride aqueous solution and are dried by anhydrous magnesium sulfate, a crude product is subjected to rotary evaporator to removal of redundant mixed solvent, and then, light yellow viscous liquid compound 2 is obtained by reduced pressure distillation, and the yield is 76.1%.
1H NMR(500MHZ,CDCl3)δ:7.41(d,1H),6.95(t,1H),6.82(d,1H),2.77(t,2H),1.36-1.18(m,8H),0.89(t,3H).13C NMR:143.3,128.2,126.5,124.1,39.2,33.1,31.9,29.4,22.7,14.2。
2-hexyl-5-tributyltin thiophene (3)
Under the protection of nitrogen, 8.4g of 2-hexylthiophene and 200mL of anhydrous tetrahydrofuran are added into a 500mL double-necked bottle, double-calandria is pumped and drained for three times, the bottle is placed at-78 ℃, 0.11mol of n-butyllithium is slowly added into a constant-pressure burette, then the bottle is slowly dripped into a reaction system, the reaction system is reacted for 30 minutes at low temperature and 40 minutes at room temperature, the bottle is placed at-78 ℃, 0.11mol of tributyltin chloride is added, the reaction is stirred overnight, 200mL of deionized water is added to stop the reaction, ether is extracted for three times, organic phases are combined, the organic phases are sequentially washed by saturated sodium chloride aqueous solution and dried by anhydrous magnesium sulfate, a crude product is subjected to rotary evaporator to removal of redundant mixed solvent, and then, light yellow viscous liquid compound 3 is obtained through reduced pressure distillation, and the yield is 80.1%.
1H NMR(500MHZ,CDCl3)δ:7.05(d,1H),6.95(d,1H),2.92(t,2H),1.75(t,2H),1.60(m,6H),1.35-1.45(m,12H),1.15(t,3H),0.95(t,9H).13C NMR:143.3，126.5，125.2，123.9，39.2，33.1，29.8，29.2，28.3，14.5。
SFX-THIO1
Under the protection of nitrogen, compound 1(190mg,0.3mmol), compound3(1.5mmol)、Pd(PPh3)4(0.03mmol) and 30mL of toluene are sequentially added into a 50mL dry double-neck bottle, the mixture is pumped and drained for three times through a double-row pipe, the mixture is placed at the temperature of 110 ℃, the mixture is stirred for reaction for 48 hours in a dark place, the mixture is cooled to the room temperature, the crude product is purified through a silica gel column chromatography after a rotary evaporator is used for removing redundant mixed solvent, and normal hexane/dichloromethane (10/1, V/V) is used as an eluent, so that the SFX-THIO1 compound is a light yellow transparent crystal.
1H NMR(500MHZ,CDCl3)δ:7.79(t,2H),7.62(t,2H),7.42(t,4H),7.37(d,2H),7.07(t,2H),6.68-6.72(m,6H),6.57(t,2H),2.79(t,8H),1.62-1.68(m,8H),1.57-1.60(m,8H),1.28-1.32(m,24H),0.90(t,12H).13C NMR:155.66,150.51,145.82,145.22,141.55,140.80,138.28,135.04,134.99,130.56,128.32,128.22,126.01,125.71,125.60,125.08,124.94,124.78,123.00,122.97,122.32,120.39,117.39,116.90,31.71,31.68,31.63,30.24,28.84,28.40,26.89,22.67,17.32,14.20,13.72。
Example 2
Synthesis of spiro [ fluorene-9, 9' -xanthene ] based organic small molecule hole transport material SFX-THIO 2:
2,2',7,7' -tetrabromo spiro [ fluorene-9, 9' -xanthene ] (1)
4-bromophenol (17.3g,100mmol), 2, 7-dibromo-9-fluorenone (3.38g,10mmol) and methanesulfonic acid (d ═ 1.48g/ml,2.6ml,3.84g,40mmol) were added to a 250ml two-necked flask under nitrogen protection, and nitrogen was purged three times with a two-necked tube, and then the mixture was heated and stirred at 150 ℃ for 24 hours, the reaction was cooled to room temperature, 100ml of a methanol solution was slowly added to the mixture, and after white crystals were precipitated, filtration was performed and washing with a large amount of methanol to obtain 1, 5.9g (yield 91%) of a white crystalline compound.
1H NMR(500MHZ,CDCl3)δ:8.00(d,2H),7.69(d,2H),7.48(d,2H),7.43(s,2H),7.30(d,2H),6.53(s,2H).13C NMR:151.49,137.21,135.20,134.42,133.31,131.14,130.60,122.53,120.29,116.70。
5-hexyl-2, 2' -bithiophene (4)
Under the protection of nitrogen, 16.6g of 2,2' -bithiophene and 200mL of anhydrous tetrahydrofuran are added into a 500mL double-necked bottle, double-calandria is pumped and drained for three times, the mixture is placed at-78 ℃, 0.11mol of n-butyl lithium is slowly added into a constant-pressure burette, then the mixture is slowly dripped into a reaction system, the reaction system is reacted for 30 minutes at low temperature and is reacted for 40 minutes at room temperature, the mixture is placed at-78 ℃, 0.11mol of 1-bromo-n-decane is added, the mixture is stirred overnight and reacted, 200mL of deionized water is added to stop the reaction, ether is extracted for three times, organic phases are combined, the mixture is sequentially washed by saturated sodium chloride aqueous solution, anhydrous magnesium sulfate is dried, a crude product is subjected to rotary evaporator to remove excessive mixed solvent, and then, and light yellow viscous liquid compound 4 is obtained through reduced pressure distillation, wherein the yield is 70.1%.
1H NMR(500MHZ,CDCl3)δ:7.31-7.34(m,1H),7.28-7.29(m,1H),7.10-7.19(m,2H),6.82-6.84(d,1H),2.95(t,2H),1.87(m,2H),1.49-1.59(m,6H),1.12(t,3H).13C NMR:145.40,138.21,135.01,127.84,124.90,123.80,123.53,123.11,31.87,31.83,30.39,29.08,22.90,14.40。
5-hexyl-5 '-tributyltin-2, 2' -bithiophene (5)
Under the protection of nitrogen, 16g of 5-hexyl-2, 2' -bithiophene and 200mL of anhydrous tetrahydrofuran are added into a 500mL double-necked bottle, double-row pipes are pumped and drained for three times, the bottle is placed at-78 ℃, 0.11mol of n-butyl lithium is slowly added into a constant-pressure burette, then the bottle is slowly dripped into a reaction system, the reaction system is reacted for 30 minutes at low temperature and is reacted for 40 minutes at room temperature, the bottle is placed at-78 ℃, 0.11mol of tributyltin chloride is added, the reaction is stirred overnight, 200mL of deionized water is added to stop the reaction, ether is extracted for three times, organic phases are combined, the organic phases are sequentially washed by saturated sodium chloride aqueous solution, anhydrous magnesium sulfate is dried, a crude product is subjected to rotary evaporator to remove excessive mixed solvent, and then, the distillation is carried out under reduced pressure to obtain a compound 5 which is a light yellow viscous liquid, and the yield is.
1H NMR(500MHZ,CDCl3)δ:7.31(d,1H),7.13(d,1H),7.07(d,1H),6.75(d,1H),2.87(t,2H),1.65-1.80(m,10H),1.40-1.49(m,14H),1.21(t,4H),1.01(m,10H).13C NMR:144.95.144.44,136.07,135.67,135.13,124.73,124.25,123.10,31.71,31.70,30.27,29.15,29.07,28.98,28.89,27.62,27.39,27.16,22.72,14.22,13.80,12.34,12.28,10.94,10.92,9.57.
SFX-THIO2
Under the protection of nitrogen, compound 1(190mg,0.3mmol), compound 5(1.5mmol), Pd (PPh)3)4(0.03mmol) and 30mL of toluene are sequentially added into a 50mL dry double-neck bottle, the mixture is pumped and drained for three times through a double-row pipe, the mixture is placed at the temperature of 110 ℃, the mixture is stirred for reaction for 48 hours in a dark place, the mixture is cooled to the room temperature, the crude product is purified through a silica gel column chromatography after a rotary evaporator is used for removing redundant mixed solvent, and normal hexane/dichloromethane (10/1, V/V) is used as an eluent, so that the SFX-THIO2 compound is a light yellow transparent crystal.
1H NMR(500MHZ,CDCl3)δ:7.85(d,2H),7.67(d,2H),7.46(t,2H),7.39(d,2H),7.31-7.33(t,2H),7.15(m,2H),6.96-7.01(m,4H),6.88(t,6H),6.65(m,6H),2.77(m,8H),1.60-1.65(m,8H),1.29-1.37(m,24H),0.87-0.92(t,12H).13C NMR:155.59,150.67,145.52,145.30,142.09,141.48,138.48,137.42,134.72,126.18,125.92,124.92,124.80,124.68,124.05,123.76,123.63,123.39,123.31,123.21,122.21，120.71,117.62，116.95，31.60,31.57,30.21,30.18,28.79,28.78,26.89,22.60,17.56,14.12,13.66。
Example 3
Synthesis of spiro [ fluorene-9, 9' -xanthene ] based organic small molecule hole transport material SFX-THIO 2:
2,2',7,7' -tetrabromo spiro [ fluorene-9, 9' -xanthene ] (1)
4-bromophenol (17.3g,100mmol), 2, 7-dibromo-9-fluorenone (3.38g,10mmol) and methanesulfonic acid (d ═ 1.48g/ml,2.6ml,3.84g,40mmol) were added to a 250ml two-necked flask under nitrogen protection, and nitrogen was purged three times with a two-necked tube, and then the mixture was heated and stirred at 150 ℃ for 24 hours, the reaction was cooled to room temperature, 100ml of a methanol solution was slowly added to the mixture, and after white crystals were precipitated, filtration was performed and washing with a large amount of methanol to obtain 1, 5.9g (yield 91%) of a white crystalline compound.
2-hexyl-5- (5- (thien-2-yl) thiophene (6)
Under the protection of nitrogen, 16g of 2, 5-di (thiophene-2-yl) thiophene and 200mL of anhydrous tetrahydrofuran are added into a 500mL double-necked bottle, double-row pipes are pumped three times, the mixture is placed at-78 ℃, 0.11mol of n-butyl lithium is slowly added into a constant-pressure burette, then the mixture is slowly dripped into a reaction system, the reaction system is reacted for 30 minutes at low temperature and 40 minutes at room temperature, the mixture is placed at-78 ℃, 0.11mol of 1-bromo-n-decane is added, the reaction is stirred overnight, 200mL of deionized water is added to stop the reaction, excessive solvent is removed through a rotary evaporator, a crude product is purified through silica gel column chromatography, and petroleum ether/dichloromethane (5/1, V/V) is used as an eluent, so that light yellow solid compound 6 is obtained, and the yield is 60.1%.
1H NMR(500MHZ,CDCl3)δ:7.21(d,1H),7.0(t,4H),6.70(d,1H),6.61(d,1H),2.57(t,2H),1.62(m,2H),1.29-1.33(m,6H),0.98(t,3H).13C NMR:143.15,137.19,136.70,134.20,127.92,126.86,125.59,125.50,120.48,43.11,32.06,31.90,29.13,22.82,14.31。
2- (5- (5-bromothien-2-yl) thien-2-yl) -5-hexylthiophene (7)
In a 250mL single-necked flask, Compound 6(6.0g,30mmol) was dissolved in 100mL of HCl3Then, NBS (6.26g,36mmol) and 5ml hoac were sequentially added, and after 3 hours of reaction at room temperature under stirring with exclusion of light, the reaction system was introduced into ice water, neutralized with sodium bicarbonate solution, extracted with diethyl ether three times, combined with organic phases, washed with saturated aqueous sodium chloride solution sequentially, dried with anhydrous sodium sulfate, the crude product was subjected to rotary evaporator to remove excess mixed solvent, purified by silica gel column chromatography, and n-hexane/dichloromethane (8/1, V/V) was used as eluent, to obtain compound 7 as a pale white solid with a yield of 96%.
1H NMR(500MHZ,CDCl3)δ:7.05(t,2H),6.90(t,1H),6.70(d,2H),6.60(d,1H),2.57(t,2H),1.62(m,2H),1.29-1.33(m,6H),0.96(t,3H).13C NMR:143.01,139.61,136.70,134.20,131.25,129.10,126.05,125.90,120.48,111.80,43.10,32.06,31.90,29.13,22.82,14.10。
2- (5- (5-hexylthiophen-2-yl) thiophen-2-yl) -5-tributyltin thiophene (8)
Under the protection of nitrogen, 13.6g of compound 7 and 200mL of anhydrous tetrahydrofuran are added into a 500mL double-necked bottle, double-calandria is pumped and drained for three times, the bottle is placed at-78 ℃, 0.11mol of n-butyllithium is slowly added into a constant-pressure burette, then the bottle is dripped into a reaction system very slowly, the reaction system reacts for 30 minutes at low temperature, the reaction system reacts for 40 minutes at room temperature, the bottle is placed at-78 ℃, 0.11mol of tributyltin chloride is added, the reaction system is stirred overnight, 200mL of deionized water is added to stop the reaction, ether is extracted for three times, organic phases are combined, the organic phases are washed by saturated sodium chloride aqueous solution in sequence, anhydrous sodium sulfate is dried, a crude product is purified by a rotary evaporator after removing excessive mixed solvent, the crude product is subjected to silica gel column chromatography, n-hexane/dichloromethane (6/1, V/V) is used as an eluent to obtain a light white solid compound 8, the yield was 53.6%.
1H NMR(500MHZ,CDCl3)δ:7.05(t,2H),6.90(t,1H),6.70(d,2H),6.60(d,1H),2.57(t,2H),1.62(m,2H),1.29-1.33(m,6H),0.96(t,3H).13C NMR:143.01,139.61,136.70,134.20,131.25,129.10,126.05,125.90,120.48,111.80,43.10,32.06,31.90,29.13,22.82,13.50。
SFX-THIO3
Under the protection of nitrogen, compound 1(190mg,0.3mmol), compound 8(1.5mmol), Pd (PPh)3)4(0.03mmol) and 30mL of toluene are sequentially added into a 50mL dry double-neck bottle, the mixture is pumped and drained for three times through a double-row pipe, the mixture is placed at the temperature of 110 ℃, the mixture is stirred for reaction for 48 hours in a dark place, the mixture is cooled to the room temperature, the crude product is purified through a silica gel column chromatography after a rotary evaporator is used for removing redundant mixed solvent, and normal hexane/dichloromethane (10/1, V/V) is used as an eluent, so that the SFX-THIO3 compound is a light yellow transparent crystal.
1H NMR(500MHZ,CDCl3)δ:7.86(d,2H),7.70(t,2H),7.47(t,2H),7.35(d,2H),7.18(m,2H),7.04(m,4H),6.94-6.99(t,12H),6.85(d,2H),6.67-6.67(t,6H),2.80(t,8H),1.65-1.70(m,8H),1.33(m,24H),0.90(t,12H)13C NMR:155.73,150.52,145.92,145.31,141.62,140.62,138.25,135.04,134.99,130.53,128.32,128.22,128.15,127.55,126.03,125.73,125.65,125.02,124.90,124.72,123.14,122.38,122.32,120.39,119.21,119.02,117.32,116.89,31.70,31.65,31.62,30.24,28.81,28.43,26.83,22.62,17.31,14.21,13.70。
Example 4
The spiro [ fluorene-9, 9' -xanthene ] derivative-based organic small-molecule hole transport materials of examples 1, 2 and 3 were applied to prepare perovskite solar cells.
The perovskite solar cell is composed of a transparent base, an electron transport layer, a hole transport layer and a counter electrode. And a light capture layer and a hole transport layer are sequentially distributed between the transparent substrate and the carbon counter electrode. The transparent substrate layer is conductive glass FTO; the electron transport layer is composed of a compact titanium dioxide layer and a mesoporous titanium dioxide layer; the light trapping layer is a perovskite layer (CsPbBr)3) (ii) a The electrode is Ag, Au or carbon. The hole-transporting layer contains spiro [ fluorene-9, 9' -xanthene-based material of the present invention]The derivative organic micromolecule hole transport material is an organic micromolecule hole transport material.
And (3) thoroughly washing the etched FTO in a detergent, acetone, isopropanol, ethanol and deionized water in an atmospheric environment. Depositing an ethanol solution of titanium isopropoxide (0.5M) and diethanolamine (0.5M, DMF) at 7000rpm for 30s, annealing at 500 deg.C in air for 2h to deposit dense TiO on the FTO glass2(c-TiO2) And (3) a layer. Prepared mesoporous TiO2(m-TiO2) (prepared by hydrothermal method) followed by c-TiO at 2000rpm2Spin coating the surface for 30s, and annealing at 450 ℃ for 30min in air. Then, c-TiO2/m-TiO20.04M TiCl at 70 ℃ for the substrate4Soaking in water solution for 30min, and annealing at 450 deg.C in air for 30 min; preparing the perovskite film by adopting a multi-step solution treatment process; 1M of PbBr2Spin coating the DMF solution to m-TiO at 2000rpm2The substrate was rotated at 90 ℃ for 30 seconds. Drying at 90 deg.CAfter 1h, 0.07MCsBr2Methanol solution in PbBr2The film is spin-coated for 30s, and the heating is continued at 250 ℃ for 5min, and the process is repeated n times (n is 1-6). The organic small molecule hole transport materials of examples 1, 2 and 3 and the classical hole transport material, Spiro-OMeTAD (2, 2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group), respectively]-9,9' -spirobifluorene) is dissolved in organic solvent toluene to prepare 0.5M HTM solution, spin-coated for 30s at 2000rmp respectively, and then heated for 10min at 80 ℃; finally, a blade coating method is adopted to deposit the HTM film with the average area of 0.09cm2The perovskite solar cell is manufactured.
Table 1 performance results for all inorganic perovskite solar cells
As shown in table 1, the device efficiencies prepared using the hole transport materials of the three structures of examples 1, 2 and 3, respectively, were better than the original device efficiency, which is consistent with the current densities of the devices. Furthermore, the cross center connected to a single bond exhibits incomplete distortion as compared with those of linear small molecules, and excessive crystallization can be suppressed. The good solubility and film-forming property enable the organic small molecule hole transport material to form good ohmic contact with an electrode, and the stability of the device can be greatly improved by using the organic small molecule hole transport material of the examples 1, 2 and 3.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (7)
1. The organic micromolecular hole transport material based on spiro [ fluorene-9, 9 '-xanthene ] is characterized in that the structural formula of the organic micromolecular hole transport material based on spiro [ fluorene-9, 9' -xanthene ] is as follows:
2. spiro [ fluorene-9, 9' -xanthene-based compounds according to claim 1]The preparation method of the organic micromolecule hole transport material is characterized by comprising the following steps: under the protection of nitrogen, 190mg,0.3mmol of compound 2,2',7,7' -tetrabromo spiro [ fluorene-9, 9' -xanthene]1.5mmol of the compound 2-hexyl-5-tributyltin thiophene, 0.03mmol of Pd (PPh)3)4And 30mL of toluene are sequentially added into a 50mL dry double-neck bottle, the mixture is pumped and discharged for three times through a double-row pipe, the mixture is placed at the temperature of 110 ℃, the mixture is stirred and reacted for 48 hours in a dark place, the mixture is cooled to the room temperature, the crude product is purified through a silica gel column chromatography after a rotary evaporator is used for removing redundant mixed solvent, and normal hexane/dichloromethane (10/1, V/V) is used as an eluent, so that a light yellow transparent crystal compound, namely a final product, is obtained.
3. The organic micromolecular hole transport material based on spiro [ fluorene-9, 9 '-xanthene ] is characterized in that the structural formula of the organic micromolecular hole transport material based on spiro [ fluorene-9, 9' -xanthene ] is as follows:
4. spiro [ fluorene-9, 9' -xanthene-based compounds according to claim 3]The preparation method of the organic micromolecule hole transport material is characterized by comprising the following steps: under the protection of nitrogen, 190mg,0.3mmol of compound 2,2',7,7' -tetrabromo spiro [ fluorene-9, 9' -xanthene]1.5mmol of 5-hexyl-5 '-tributyltin-2, 2' -bithiophene, 0.03mmol of Pd (PPh)3)4Adding 30mL of toluene into a 50mL dry double-neck bottle in sequence, pumping and discharging for three times through a double-row pipe, placing the mixture at the temperature of 110 ℃, stirring the mixture for reaction for 48 hours in a dark place, cooling the mixture to room temperature, removing the redundant mixed solvent from the crude product through a rotary evaporator, and then obtaining the crude productPurifying the crude product by silica gel column chromatography, and using n-hexane/dichloromethane (10/1, V/V) as eluent to obtain a light yellow transparent crystal compound, namely the final product.
5. The organic micromolecular hole transport material based on spiro [ fluorene-9, 9 '-xanthene ] is characterized in that the structural formula of the organic micromolecular hole transport material based on spiro [ fluorene-9, 9' -xanthene ] is as follows:
6. spiro [ fluorene-9, 9' -xanthene-based compounds according to claim 5]The preparation method of the organic micromolecule hole transport material is characterized by comprising the following steps: under the protection of nitrogen, 190mg,0.3mmol of compound 2,2',7,7' -tetrabromo spiro [ fluorene-9, 9' -xanthene]1.5mmol of the compound 2- (5- (5-hexylthiophen-2-yl) thiophen-2-yl) -5-tributylstannothiophene, 0.03mmol of Pd (PPh)3)4And 30mL of toluene are sequentially added into a 50mL dry double-neck bottle, the mixture is pumped and discharged for three times through a double-row pipe, the mixture is placed at the temperature of 110 ℃, the mixture is stirred and reacted for 48 hours in a dark place, the mixture is cooled to the room temperature, the crude product is purified through a silica gel column chromatography after a rotary evaporator is used for removing redundant mixed solvent, and normal hexane/dichloromethane (10/1, V/V) is used as an eluent, so that a light yellow transparent crystal compound, namely a final product, is obtained.
7. Use of a spiro [ fluorene-9, 9' -xanthene ] based organic small molecule hole transport material according to any of claims 1, 3 or 5 for the preparation of perovskite solar cells.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011108261.7A CN112250677A (en) | 2020-10-16 | 2020-10-16 | Organic small molecule hole transport material based on spiro [ fluorene-9, 9' -xanthene ], preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011108261.7A CN112250677A (en) | 2020-10-16 | 2020-10-16 | Organic small molecule hole transport material based on spiro [ fluorene-9, 9' -xanthene ], preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112250677A true CN112250677A (en) | 2021-01-22 |
Family
ID=74243729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011108261.7A Pending CN112250677A (en) | 2020-10-16 | 2020-10-16 | Organic small molecule hole transport material based on spiro [ fluorene-9, 9' -xanthene ], preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112250677A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087726A (en) * | 2021-02-24 | 2021-07-09 | 浙江大学 | Arylamine organic semiconductor material and application thereof in photoelectric device |
| CN115386083A (en) * | 2022-09-16 | 2022-11-25 | 河南农业大学 | 3, 4-ethylenedioxythiophene covalent triazine framework and synthesis method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440082A (en) * | 2008-12-12 | 2009-05-27 | 南京邮电大学 | Spirofluorene xanthene material, and preparation and use thereof |
| CN102786508A (en) * | 2012-07-19 | 2012-11-21 | 南京邮电大学 | Spiro-fluorene-9,9-xanthene bipolar luminescent material, its preparation method and its application method |
| CN106977491A (en) * | 2017-01-25 | 2017-07-25 | 孙立成 | Spiro [ fluorene-9, 9-xanthene ] hole transport material and application thereof |
| CN107365411A (en) * | 2017-07-07 | 2017-11-21 | 南方科技大学 | A kind of hole transmission layer containing organic conjugate polymer semi-conducting material and application thereof |
| CN108299407A (en) * | 2017-12-29 | 2018-07-20 | 太原理工大学 | Spiral shell [fluorenes -9,9 '-xanthene] derivative and its preparation based on the substitution of more sulphur fulvalenes and application |
| US20180366539A1 (en) * | 2016-03-09 | 2018-12-20 | The Regents Of The University Of California | Graded bandgap perovskite solar cell |
| CN109912562A (en) * | 2019-03-20 | 2019-06-21 | 南昌航空大学 | A kind of cross type small organic molecule hole mobile material and preparation method |
| CN111153894A (en) * | 2020-01-05 | 2020-05-15 | 浙江大学 | Arylamine compound and application thereof in photoelectric device |
-
2020
- 2020-10-16 CN CN202011108261.7A patent/CN112250677A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440082A (en) * | 2008-12-12 | 2009-05-27 | 南京邮电大学 | Spirofluorene xanthene material, and preparation and use thereof |
| CN102786508A (en) * | 2012-07-19 | 2012-11-21 | 南京邮电大学 | Spiro-fluorene-9,9-xanthene bipolar luminescent material, its preparation method and its application method |
| US20180366539A1 (en) * | 2016-03-09 | 2018-12-20 | The Regents Of The University Of California | Graded bandgap perovskite solar cell |
| CN106977491A (en) * | 2017-01-25 | 2017-07-25 | 孙立成 | Spiro [ fluorene-9, 9-xanthene ] hole transport material and application thereof |
| CN107365411A (en) * | 2017-07-07 | 2017-11-21 | 南方科技大学 | A kind of hole transmission layer containing organic conjugate polymer semi-conducting material and application thereof |
| CN108299407A (en) * | 2017-12-29 | 2018-07-20 | 太原理工大学 | Spiral shell [fluorenes -9,9 '-xanthene] derivative and its preparation based on the substitution of more sulphur fulvalenes and application |
| CN109912562A (en) * | 2019-03-20 | 2019-06-21 | 南昌航空大学 | A kind of cross type small organic molecule hole mobile material and preparation method |
| CN111153894A (en) * | 2020-01-05 | 2020-05-15 | 浙江大学 | Arylamine compound and application thereof in photoelectric device |
Non-Patent Citations (2)
| Title |
|---|
| BUKET BEZGIN CARBAS: "New fluorene–xanthene-based hybrid electrochromic and fluorescent polymers via donor–acceptor approach", 《ELECTROCHIMICA ACTA》 * |
| VALERIE A. CHIYKOWSKI: "Precise Control of Thermal and Redox Properties of Organic Hole- Transport Materials", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087726A (en) * | 2021-02-24 | 2021-07-09 | 浙江大学 | Arylamine organic semiconductor material and application thereof in photoelectric device |
| CN115386083A (en) * | 2022-09-16 | 2022-11-25 | 河南农业大学 | 3, 4-ethylenedioxythiophene covalent triazine framework and synthesis method and application thereof |
| CN115386083B (en) * | 2022-09-16 | 2024-02-27 | 河南农业大学 | 3, 4-ethylenedioxythiophene covalent triazine framework and synthetic method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107074830B (en) | Difluorobithiophene-based D-A polymers for photovoltaic applications | |
| EP2072557A1 (en) | Electron-donating organic material for photovoltaic devices, material for photovoltaic devices, and photovoltaic devices | |
| JP6797019B2 (en) | Coupled polymers and devices incorporating them | |
| CN104672434B (en) | A kind of organic semiconducting materials and preparation method and application | |
| CN108467402A (en) | Fluorine replaces organic molecule hole mobile material and its application | |
| Zhou et al. | Enhancing the photovoltaic performance of triphenylamine based star-shaped molecules by tuning the moiety sequence of their arms in organic solar cells | |
| TWI671303B (en) | Design and synthesis of porphyrin materials for highly efficient organic photovoltaics | |
| CN103857724B (en) | The method comprising the polymer of benzo miscellaneous [1,3] diazole unit for preparation | |
| CN105017264A (en) | Organic small molecular photoelectric functional material, and preparation method thereof | |
| CN101787020A (en) | Organic conjugated molecule capable of being processed by solution and application thereof in solar cells | |
| CN112250677A (en) | Organic small molecule hole transport material based on spiro [ fluorene-9, 9' -xanthene ], preparation method and application thereof | |
| KR101484007B1 (en) | new organic semiconductor compound and a method for manufacturing the same | |
| Qiu et al. | An asymmetric small molecule based on thieno [2, 3-f] benzofuran for efficient organic solar cells | |
| CN115819457A (en) | Carbazole organic micromolecule hole transport material containing phosphonic acid and methylthio, and preparation method and application thereof | |
| EP2532696A1 (en) | Conjugated fluorene polymer, preparing method thereof and solar battery component | |
| CN110143976B (en) | Synthesis method and application of branched porphyrin-perylene diimide-based small molecule receptor | |
| CN113527641B (en) | Polymer material based on ester side chain substituted quinoxaline derivative and application thereof | |
| Adhikari et al. | Solid-state showdown: Comparing the photovoltaic performance of amorphous and crystalline small-molecule diketopyrrolopyrrole acceptors | |
| KR101553806B1 (en) | Organic semiconductor compounds Containing Posphine oxide and Solar Cell Device Using This Material | |
| CN112142758A (en) | Organic small molecule hole transport material based on benzodithiophene and preparation method and application thereof | |
| CN110218296B (en) | Structure, synthesis and application of carbazole polymer hole transport material | |
| CN109776767B (en) | Conjugated polymer containing difluoronaphthothiophene diketone electron-withdrawing unit and synthetic method and application thereof | |
| JP2019006770A (en) | Novel porphyrin derivative, method for producing same, donor material, photo/electric conversion device, and method for producing same | |
| CN115612310B (en) | Porphyrin photosensitive dye and application thereof | |
| CN110790760B (en) | Fluorohydroxyquinolyl metal organic small molecular complex with aromatic group bridging naphthalimide and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210122 |
|
| WD01 | Invention patent application deemed withdrawn after publication |