CN109503457A - Dinaphtho heterocycle small molecule hole transport material, synthetic method and its application - Google Patents
Dinaphtho heterocycle small molecule hole transport material, synthetic method and its application Download PDFInfo
- Publication number
- CN109503457A CN109503457A CN201811304172.2A CN201811304172A CN109503457A CN 109503457 A CN109503457 A CN 109503457A CN 201811304172 A CN201811304172 A CN 201811304172A CN 109503457 A CN109503457 A CN 109503457A
- Authority
- CN
- China
- Prior art keywords
- dinaphtho
- hole transport
- solution
- compound
- layer
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 38
- 230000005525 hole transport Effects 0.000 title claims abstract description 23
- -1 heterocycle small molecule Chemical class 0.000 title claims abstract description 15
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- YFIJJNAKSZUOLT-UHFFFAOYSA-N Anthanthrene Chemical compound C1=C(C2=C34)C=CC=C2C=CC3=CC2=CC=CC3=CC=C1C4=C32 YFIJJNAKSZUOLT-UHFFFAOYSA-N 0.000 claims abstract description 52
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002240 furans Chemical class 0.000 claims abstract description 11
- 150000003384 small molecules Chemical class 0.000 claims abstract description 8
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 47
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 238000004528 spin coating Methods 0.000 claims description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000005540 biological transmission Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- KYUIIGJSSHTWDW-UHFFFAOYSA-N 2,3-dimethoxy-n-phenylaniline Chemical class COC1=CC=CC(NC=2C=CC=CC=2)=C1OC KYUIIGJSSHTWDW-UHFFFAOYSA-N 0.000 claims description 6
- AGJLZAWPAODMHX-UHFFFAOYSA-N C(C)(C)(C)P(C(C)(C)C)C(C)(C)C.B(O)(O)O Chemical compound C(C)(C)(C)P(C(C)(C)C)C(C)(C)C.B(O)(O)O AGJLZAWPAODMHX-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000000280 densification Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 125000000468 ketone group Chemical group 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 5
- 239000012047 saturated solution Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000012296 anti-solvent Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 238000005118 spray pyrolysis Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000004896 high resolution mass spectrometry Methods 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 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 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013495 cobalt Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002994 raw material 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/06—Peri-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- 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
- 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
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- 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
Abstract
The present invention relates to perovskite solar cell technical fields, it is desirable to provide a kind of dinaphtho heterocycle small molecule hole transport material, synthetic method and its application.The effective component of the material is any one in dioxa anthanthrene, dithia anthanthrene, dinaphtho furans, dinaphthyl bithiophene or dinaphtho pyrroles.The present invention is using dioxa anthanthrene, dithia anthanthrene, dinaphtho furans, dinaphthyl bithiophene and dinaphtho pyrroles as core, and by introducing dialkoxy diphenylamino group on active site, design has synthesized five kinds of small molecule hole transport materials.Materials synthesis of the present invention is low in cost, good film-forming property, hole mobility are high, can be used as undoped hole mobile material applied to perovskite solar cell device, obtains higher device efficiency.
Description
Technical field
The invention belongs to perovskite solar cell technical fields, and in particular to five class dinaphtho heterocycle small molecule hole transports
Material and its synthetic method and application.
Background technique
2009, Miyasaka group took the lead in being applied to the sun using hybrid inorganic-organic perovskite as light absorbing material
In battery, the energy conversion efficiency of battery is up to 3.8%, has caused extensive research in the world, related such novel sun
The report of battery increases in blowout, until 23.3% energy conversion efficiency is had been achieved within 2018, more than 1cm2Device it is real
19.6% energy conversion efficiency (Science, 2016,353,58-62) is showed.At the same time, the perovskite that solution is processed is too
Positive electricity pond can realize efficient, large-scale serial production by roll-to-roll, compared to traditional silica-based solar cell, system
It makes that at low cost, processing technology is simple, there is good commercial promise.Hole transport materials facilitate perovskite solar cell structure
Interface is adjusted, and for reducing charge recombination, is accelerated hole transport to play the role of critical, can be effectively improved perovskite too
The energy conversion efficiency in positive electricity pond.
In the prior art, most widely used organic hole conveying material is mainly 2,2 ', 7 in perovskite solar cell,
7 '-four [N, N- bis- (4- methoxyphenyl) amino] two fluorenes of -9,9 '-spiral shell (spiro-OMeTAD).But spiro-OMeTADization
Structure is complicated, synthetic route is long, expensive, while the material hole mobility is lower, so as to cause perovskite sun electricity
Pond energy conversion efficiency is low.It is usually necessary to use bis- (trifluoromethanesulp-onyl -onyl imide) lithiums (LiTFSI), tert .-butylpyridine (TBP) with
And bis- (trifluoromethanesulp-onyl -onyl imide) cobalts (FK209) carry out p-type doping to improve hole mobility, but this kind of doping will lead to electricity
Pond device performance is unstable, while Master Cost is expensive.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide five small point of class dinaphtho heterocycles
Sub- hole mobile material and its synthetic method and application.
In order to solve the technical problem, solution of the invention is:
Five class dinaphtho heterocycle small molecule hole transport materials are provided, the effective component of the material be dioxa anthanthrene,
Any one in dithia anthanthrene, dinaphtho furans, dinaphthyl bithiophene or dinaphtho pyrroles, chemical structural formula is respectively such as
Shown in I~formula of formula V:
Wherein, R is the alkyl of C1~C6.
As a preferred solution of the present invention, in the chemical structural formula of each compound, R is the alkyl of C1~C6.
Invention further provides the preparation methods of aforementioned five classes dinaphtho heterocycle small molecule hole transport material, including
Following step:
(1) synthesis of intermediate
(1.1) dioxa anthanthrene, dithia anthanthrene, dinaphthyl [2,1-b:1', 2'-d] and furans, dinaphthyl [2,1- are taken
B:1', 2'-d] bithiophene, the dinaphthyl [2,1-b:1', 2'-d] of alkoxy substitution and pyrroles, it is separately added into methylene chloride and obtains
Respective methylene chloride saturated solution；
(1.2) under the conditions of -78 DEG C, bromine water is added drop-wise in the methylene chloride saturated solution of dioxa anthanthrene, is obtained
Mixed solution；Then room temperature is warmed naturally to, as reaction carries out generation solid；It filters, washing obtains intermediate compound I；Bromine water with
The molar ratio of dioxa anthanthrene is 2: 1；
(1.3) it is operated in the same way, respectively obtains intermediate II, intermediate III, intermediate IV or intermediate V；
(2) synthesis of compound
(2.1) in molar ratio 2: 4.4: 0.1: 0.2: 6 by intermediate I and dimethoxy diphenylamines, three (dibenzylidenes third
Ketone) two palladiums, tetrafluoro boric acid tri-tert-butylphosphine and potassium tert-butoxide be added in toluene together；Under the protection of nitrogen, while stirring
110 DEG C are heated to, 2h is reacted；Standing is cooled to room temperature, and is filtered out organic solvent and is obtained product crude product；It purifies, obtains by chromatographic column
To compound I；
(1.2) it is operated in the same way, respectively obtains compound ii, compound III, compounds Ⅳ or compound V；
The synthetic route of each compound is as follows:
In above-mentioned reaction equation, R is C1~C6 alkyl.
Invention further provides the application methods of aforementioned small molecule hole transport material, are as undoped
Hole mobile material is applied to perovskite solar cell device；The perovskite solar cell device has five-layer structure, by
Under supreme be followed successively by FTO glass substrate, densification TiO2Layer, porous TiO2Layer, calcium titanium ore bed, hole transmission layer and metal electrode,
Hole-transporting layer is made of the small molecule hole transport material.
The present invention also provides the sides that perovskite solar cell device is prepared using aforementioned small molecule hole transport material
Method, comprising the following steps:
(1) it cleans
It is successively dense with 1% mass after cleaning the pollutant (such as dust) of surface attachment of FTO glass substrate with detergent
Surfactant solution, water and the EtOH Sonicate of degree are to remove organic pollutant；After being dried with nitrogen, then with ultraviolet-ozone at
30min is managed, guarantees that surface is clean, cleans；
(2) densification TiO is prepared2Layer
Under conditions of 450 DEG C, the butanol solution of bis- (levulinic ketone group) diisopropyl titanate esters is passed through into spray pyrolysis
It is deposited in clean FTO glass substrate；After being cooled to room temperature, TiO is obtained2/ FTO substrate；
(3) porous TiO is prepared2Layer
In TiO2Spin coating is by TiO in/FTO substrate2After the suspension that slurry and ethyl alcohol are made into, the dry 10min at 100 DEG C；
The calcination 30min at 450 DEG C, forms porous TiO2Layer；
(4) calcium titanium ore bed is prepared
By FAI, PbI2, MABr and PbBr2, CsI be mixed in the DMF of volume ratio 4: 1: in DMSO solution, obtain Cs0.05
(FA0.83MA0.17)0.95Pb(I0.83Br0.17) precursor solution；Then calcium titanium ore bed is prepared by two step spin-coating steps；Two step spin coatings
When, 10s is rotated with 1000rpm speed respectively and 20s is rotated with 6000rpm speed；In the last 5s of second of spin coating process
Chlorobenzene anti-solvent is added dropwise；Then, substrate is dried into 1h under the conditions of 100 DEG C, calcium titanium ore bed is made；
(5) hole transmission layer is prepared
It is 15mg/mL solution that chemical compounds I, which is added in chlorobenzene, and is configured to concentration, then by solution with the speed of 6000rpm
Spin coating 30s is deposited on calcium titanium ore bed；
Chemical compounds I is replaced with into any one in compound ii, compound III, compounds Ⅳ or compound V, it can
The hole transmission layer of corresponding ingredient is made；
(6) it is placed in vacuum evaporation room, metal electrode is deposited to hole transport layer surface by vacuum vapour deposition, calcium is made
Titanium ore solar cell device.
In the present invention, in the butanol solution of bis- (levulinic ketone group) diisopropyl titanate esters of the step (2), bis- (second
Acyl acetonyl) volume ratio of diisopropyl titanate esters and butanol is 1: 10.
In the present invention, in the step (3), TiO2The mass ratio of slurry and ethyl alcohol is 1: 6.
In the present invention, in the precursor solution in step (4), FAI concentration is 0.95M, PbI2Concentration is 1M, MABr concentration
For 0.2M, PbBr2Concentration is 0.2M, and CsI concentration is 0.06M.
Inventive principle summary:
The present invention is with dioxa anthanthrene, dithia anthanthrene, dinaphtho furans, dinaphthyl bithiophene and dinaphtho pyrroles
Core, by introducing dialkoxy diphenylamino group on active site, design has synthesized five kinds of small molecule hole transport materials.This
Invention materials synthesis is low in cost, good film-forming property, hole mobility are high, can be used as undoped hole mobile material applied to calcium
Titanium ore solar cell device obtains higher device efficiency.
Compared with prior art, the beneficial effects of the present invention are:
(1) dioxa anthanthrene of the invention, dithia anthanthrene, dinaphtho furans, dinaphthyl bithiophene and dinaphtho pyrrole
Five micromolecular hole mobile materials are coughed up, preparation process is simple, raw material is easy to get, is cheap, is particularly suitable for industrialized production.
(2) dioxa anthanthrene of the invention, dithia anthanthrene, dinaphtho furans, dinaphthyl bithiophene and dinaphtho pyrrole
Cough up five micromolecular hole mobile materials, glass transition temperature is higher, better heat stability, can be formed amorphous well
Film is conducive to the environmental stability for promoting solar battery.
(3) dioxa anthanthrene of the invention, dithia anthanthrene, dinaphtho furans, dinaphthyl bithiophene and dinaphtho pyrrole
Coughing up five micromolecular hole mobile materials can be applied in perovskite solar cell device without adulterating any additive,
The photoelectric conversion efficiency of device is higher than 19.8%, illustrates that these five types of compounds of the present invention are the hole transport materials of function admirable
Material.
Detailed description of the invention
Fig. 1 is using five micromolecular of the present invention as perovskite solar cell device made of hole mobile material
Structural schematic diagram.
Fig. 2 is using five micromolecular of the present invention as perovskite solar cell device made of hole mobile material
Matter figure (abscissa refers to that voltage, ordinate refer to current density).
Specific embodiment
The present invention is further explained in the light of specific embodiments.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Embodiment 1
The preparation (synthetic route is as shown in Summary) of chemical compounds I:
The synthesis of intermediate I: dioxa anthanthrene (2.86g, 10mmol) is dissolved in the methylene chloride of 2L, is saturated
Solution；Bromine (3.2g, 20mmol) is slowly added dropwise under the conditions of -78 DEG C.By obtained mixed solution in 5 in stirring
It is slowly increased to room temperature in hour, reaction 2 hours is stirred at room temperature.It is carried out with reaction, yellow solid is precipitated in reaction system.It takes out
The solid that filter, washing generate obtains intermediate I (4.36g, 99% yield).
The synthesis of chemical compounds I: by intermediate I (880mg, 2mmol) and dimethoxy diphenylamines (1.08g, 4.4mmol),
Tris(dibenzylideneacetone) dipalladium (91mg, 0.1mmol), tetrafluoro boric acid tri-tert-butylphosphine (58mg, 0.2mmol) and sodium tert-butoxide
(577mg, 6mmol) is added to together in the toluene of 50mL；Under the protection of nitrogen, it is heated to 110 DEG C while stirring, reaction
2h, rear stand are cooled to room temperature, are extracted with saturated salt solution and methylene chloride, then dried, filtered with anhydrous magnesium sulfate, and remove
Organic solvent obtains product crude product, and by column chromatographic purifying, obtains chemical compounds I (1.25g, 85% yield).1H NMR
(500MHz,[d8] THF): δ=7.33 (d, J=9.3Hz, 2H), 6.92-6.85 (m, 8H), 6.83 (dd, J=8.7,1.5Hz,
4H), 6.78-6.74 (m, 8H), 6.65 (d, J=8.2Hz, 2H), 3.71ppm (s, 12H)13C NMR(126MHz,[d8]THF)
δ=156.13,150.60,145.49,143.05,139.35,128.95,127.27,125.23,124.12,123.53,
117.90,115.26,112.08,110.36,55.59ppm.HR-MS(MALDI-TOF)m/z calcd.for(C48H36N2O6):
736.25734.Found:736.25678.
Embodiment 2
The preparation (synthetic route is as shown in Summary) of compound ii:
The synthesis of intermediate II: dithia anthanthrene (3.14g, 10mmol) is dissolved in the methylene chloride of 3L, is satisfied
And solution；Bromine (3.2g, 20mmol) is slowly added dropwise under the conditions of -78 DEG C.By obtained mixed solution in 5 in stirring
It is slowly increased to room temperature in a hour, reaction 2 hours is stirred at room temperature.It is carried out with reaction, red solid is precipitated in reaction system.
It filters, the solid that washing generates obtains intermediate II (4.63g, 98% yield).
The synthesis of compound ii: by intermediate II (944mg, 2mmol) and dimethoxy diphenylamines (1.08g,
4.4mmol), tris(dibenzylideneacetone) dipalladium (91mg, 0.1mmol), tetrafluoro boric acid tri-tert-butylphosphine (58mg, 0.2mmol)
It is added in the toluene of 50mL together with sodium tert-butoxide (577mg, 6mmol), under the protection of nitrogen, side stirring, which becomes, to be heated to
110 DEG C, 2h is reacted, rear stand is cooled to room temperature, is extracted with saturated salt solution and methylene chloride, then dry with anhydrous magnesium sulfate,
Filtering, and organic solvent is removed, product crude product is obtained, and by column chromatographic purifying, obtaining compound ii, (1.34g, 87% is produced
Rate).1H NMR(500MHz,[d8] THF): δ=7.33 (d, J=9.3Hz, 2H), 6.92-6.85 (m, 8H), 6.83 (dd, J=
8.7,1.5Hz, 4H), 6.78-6.74 (m, 8H), 6.65 (d, J=8.2Hz, 2H), 3.71ppm (s, 12H)13C NMR
(126MHz,[d8] THF) δ=156.13,150.60,145.49,143.05,139.35,128.95,127.27,125.23,
124.12,123.53,117.90,115.26,112.08,110.36,55.59ppm.HR-MS(MALDI-TOF)m/z
calcd.for(C48H36N2O6):736.25734.Found:736.25678.
Embodiment 3
The preparation (synthetic route is as shown in Summary) of compound III:
The synthesis of intermediate III: dinaphtho furans (2.68g, 10mmol) is dissolved in the methylene chloride of 100mL, is satisfied
And solution；Bromine (3.2g, 20mmol) is slowly added dropwise under the conditions of -78 DEG C.By obtained mixed solution in 5 in stirring
It is slowly increased to room temperature in a hour, reaction 2 hours is stirred at room temperature.It is carried out with reaction, white solid is precipitated in reaction system.
It filters, the solid that washing generates obtains intermediate III (4.18g, 99% yield).
The synthesis of compound III: by intermediate III (846mg, 2mmol) and dimethoxy diphenylamines (1.08g,
4.4mmol), tris(dibenzylideneacetone) dipalladium (91mg, 0.1mmol), tetrafluoro boric acid tri-tert-butylphosphine (58mg, 0.2mmol)
It is added in the toluene of 50mL together with sodium tert-butoxide (577mg, 6mmol), under the protection of nitrogen, side stirring, which becomes, to be heated to
110 DEG C, 2h is reacted, rear stand is cooled to room temperature, is extracted with saturated salt solution and methylene chloride, then dry with anhydrous magnesium sulfate,
Filtering, and organic solvent is removed, product crude product is obtained, and by column chromatographic purifying, obtaining compound III, (1.29g, 89% is produced
Rate).1H NMR(400MHz,THF-d8) δ=9.15 (d, J=8.5Hz, 2H), 8.27 (dd, J=8.5,1.2Hz, 2H), 7.68
(ddd, J=8.3,6.8,1.3Hz, 2H), 7.50 (s, 2H), 7.41 (ddd, J=8.1,6.9,1.0Hz, 2H), 6.99-6.91
(m,8H),6.82–6.74(m,8H),3.71ppm(s,12H).13C NMR(101MHz,THF-d8) δ=155.36,154.81,
144.96,142.70,129.46,128.63,126.17,126.10,125.68,124.36,123.66,116.82,114.33,
111.82,54.56ppm.HR-MS(MALDI-TOF)m/z calcd.for(C48H38N2O5):722.84100.Found:
722.84093.
Embodiment 4
The preparation (synthetic route is as shown in Summary) of compounds Ⅳ:
The synthesis of intermediate IV: dinaphthyl bithiophene (2.84g, 10mmol) is dissolved in the methylene chloride of 100mL, is satisfied
And solution；Bromine (3.2g, 20mmol) is slowly added dropwise under the conditions of -78 DEG C.By obtained mixed solution in 5 in stirring
It is slowly increased to room temperature in a hour, reaction 2 hours is stirred at room temperature.It is carried out with reaction, white solid is precipitated in reaction system.
It filters, the solid that washing generates obtains intermediate III (4.28g, 97% yield).
The synthesis of compounds Ⅳ: by intermediate IV (884mg, 2mmol) and dimethoxy diphenylamines (1.08g,
4.4mmol), tris(dibenzylideneacetone) dipalladium (91mg, 0.1mmol), tetrafluoro boric acid tri-tert-butylphosphine (58mg, 0.2mmol)
It is added in the toluene of 50mL together with sodium tert-butoxide (577mg, 6mmol), under the protection of nitrogen, side stirring, which becomes, to be heated to
110 DEG C, 2h is reacted, rear stand is cooled to room temperature, is extracted with saturated salt solution and methylene chloride, then dry with anhydrous magnesium sulfate,
Filtering, and organic solvent is removed, product crude product is obtained, and by column chromatographic purifying, obtaining compounds Ⅳ, (1.23g, 83% is produced
Rate).1H NMR(400MHz,THF-d8) δ=8.86 (dd, J=8.5,1.2Hz, 2H), 8.21 (dd, J=8.4,1.4Hz, 2H),
7.61 (s, 2H), 7.48 (ddd, J=8.4,6.8,1.4Hz, 2H), 7.40 (ddd, J=8.1,6.8,1.1Hz, 2H), 7.01-
6.89(m,9H),6.84–6.72(m,8H),3.72ppm(s,12H).13C NMR (101MHz, THF) δ=155.40,143.94,
142.65,138.53,130.98,129.47,128.76,126.16,125.53,125.08,124.63,123.89,119.16,
114.35,54.57ppm.HR-MS(MALDI-TOF)m/z calcd.for(C48H38N2O4S):738.90200.Found:
738.90176.
Embodiment 5
Chemical compounds I, compound ii, compound III, compounds Ⅳ or compound V are respectively as hole mobile material, application
In perovskite solar cell device.
Using chemical compounds I of the present invention, compound ii, compound III, compounds Ⅳ and compound V as sky
The titanium ore solar cell device of cave transport layer preparation, comprising: FTO glass substrate, densification TiO2Layer, porous TiO2Layer, perovskite
Layer, hole transmission layer and metal electrode, wherein FTO glass substrate is by glass substrate and FTO cathode (fluorine-doped tin oxide glass
Electrode) composition, fine and close TiO2Layer and porous TiO2Layer is used as TiO2Electron transfer layer, calcium titanium ore bed is as light-absorption layer.
Embodiment 6
The preparation of perovskite solar cell device
1) clean: then the pollutants such as dust adhered to first with the surface that detergent cleans FTO glass substrate are used respectively
Surfactant solution, water and the EtOH Sonicate of 1% mass concentration of 15mL are to remove organic pollutant, clean FTO glass
The clean transparent conductive substrate in surface can be obtained with being dried with nitrogen in substrate, then handles 30min with ultraviolet-ozone, guarantees it
Surface is clean, cleans；
2) densification TiO is prepared2Layer: under conditions of 450 DEG C, by volume for 1: 10 will be bis- (levulinic ketone group) diisopropyl
Base titanate esters are dissolved in butanol, and solution is deposited in clean FTO glass substrate by spray pyrolysis, after cooling room temperature, are obtained
To TiO2/ FTO substrate；
3) porous TiO is prepared2Layer: in TiO obtained above2Spin coating TiO in/FTO substrate2Slurry and ethyl alcohol are made into outstanding
Turbid (TiO2The mass ratio of slurry and ethyl alcohol is 1: 6), then dry 10min, calcination 30min, shape at 450 DEG C at 100 DEG C
At porous TiO2Layer；
4) calcium titanium ore bed is prepared: by FAI, PbI2, MABr and PbBr2, CsI is mixed in DMF:DMSO=4:1 (v:v)
The 1.2M Cs arrived0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17) precursor solution, FAI concentration is 0.95M in precursor solution,
PbI2Concentration is 1M, and MABr concentration is 0.2M, PbBr2Concentration is 0.2M, and CsI concentration is 0.06M.Pass through two step spin-coating step systems
Standby calcium titanium ore bed, two step spin coatings rotate 10s respectively with 1000rpm speed and rotate 20s with 6000rpm speed, revolve at second
Chlorobenzene anti-solvent is added dropwise in the last 5s of painting process；Then, required perovskite is made after drying 1h under the conditions of 100 DEG C in substrate
Layer；
5) prepare hole transmission layer: it is 15mg/mL solution that chemical compounds I, which is added in chlorobenzene, and is configured to concentration, then by institute
The solution of configuration is deposited on calcium titanium ore bed with the speed spin coating 30s of 6000rpm；
Chemical compounds I is replaced with into any one in compound ii, compound III, compounds Ⅳ or compound V, it can
The hole transmission layer of corresponding ingredient is made；
6) it is placed in vacuum evaporation room, metal electrode is deposited to hole transport layer surface by vacuum vapour deposition, calcium is made
Titanium ore solar cell device.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe
Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to the above reality
Any simple modifications, equivalent substitutions and improvements etc. made by example are applied, it is fallen within the scope of protection of the technical scheme of the present invention
It is interior.
Claims (8)
1. dinaphtho heterocycle small molecule hole transport material, which is characterized in that the effective component of the material be dioxa anthanthrene,
Any one in dithia anthanthrene, dinaphtho furans, dinaphthyl bithiophene or dinaphtho pyrroles, chemical structural formula is respectively such as
Shown in I~formula of formula V:
Wherein, R is the alkyl of C1~C6.
2. five classes dinaphtho heterocycle small molecule hole transport material according to claim 1, which is characterized in that each compound
Chemical structural formula in, R be C1~C6 alkyl.
3. the preparation method of five classes dinaphtho heterocycle small molecule hole transport material as claimed in claim 1 or 2, which is characterized in that
Include the following steps:
(1) synthesis of intermediate
(1.1) take dioxa anthanthrene, dithia anthanthrene, dinaphthyl [2,1-b:1', 2'-d] and furans, dinaphthyl [2,1-b:1',
2'-d] bithiophene, the dinaphthyl [2,1-b:1', 2'-d] of alkoxy substitution and pyrroles, it is separately added into methylene chloride and obtains respectively
Methylene chloride saturated solution；
(1.2) under the conditions of -78 DEG C, bromine water is added drop-wise in the methylene chloride saturated solution of dioxa anthanthrene, is mixed
Solution；Then room temperature is warmed naturally to, as reaction carries out generation solid；It filters, washing obtains intermediate compound I；Bromine water and dioxy
The molar ratio of miscellaneous anthanthrene is 2: 1；
(1.3) it is operated in the same way, respectively obtains intermediate II, intermediate III, intermediate IV or intermediate V；
(2) synthesis of compound
(2.1) in molar ratio 2: 4.4: 0.1: 0.2: 6 by intermediate I and dimethoxy diphenylamines, three (dibenzalacetones) two
Palladium, tetrafluoro boric acid tri-tert-butylphosphine and potassium tert-butoxide are added in toluene together；Under the protection of nitrogen, it is heated to while stirring
110 DEG C, react 2h；Standing is cooled to room temperature, and is filtered out organic solvent and is obtained product crude product；It is purified by chromatographic column, obtains chemical combination
Object I；
(1.2) it is operated in the same way, respectively obtains compound ii, compound III, compounds Ⅳ or compound V.
4. the application method of small molecule hole transport material described in claim 1, which is characterized in that be as undoped
Hole mobile material is applied to perovskite solar cell device；The perovskite solar cell device has five-layer structure, by
Under supreme be followed successively by FTO glass substrate, densification TiO2Layer, porous TiO2Layer, calcium titanium ore bed, hole transmission layer and metal electrode,
Hole-transporting layer is made of the small molecule hole transport material.
5. special using the method that small molecule hole transport material prepares perovskite solar cell device described in claim 1
Sign is, comprising the following steps:
(1) it cleans
After cleaning the pollutant of surface attachment of FTO glass substrate with detergent, successively with the surfactant of 1% mass concentration
Solution, water and EtOH Sonicate are to remove organic pollutant；After being dried with nitrogen, then with ultraviolet-ozone processing 30min, guarantee table
Face is clean, cleans；
(2) densification TiO is prepared2Layer
Under conditions of 450 DEG C, will be bis- (levulinic ketone group) diisopropyl titanate esters butanol solution pass through spray pyrolysis deposit
In clean FTO glass substrate；After being cooled to room temperature, TiO is obtained2/ FTO substrate；
(3) porous TiO is prepared2Layer
In TiO2Spin coating is by TiO in/FTO substrate2After the suspension that slurry and ethyl alcohol are made into, the dry 10min at 100 DEG C；?
Calcination 30min at 450 DEG C, forms porous TiO2Layer；
(4) calcium titanium ore bed is prepared
By FAI, PbI2, MABr and PbBr2, CsI be mixed in the DMF of volume ratio 4: 1: in DMSO solution, obtain Cs0.05
(FA0.83MA0.17)0.95Pb(I0.83Br0.17) precursor solution；Then calcium titanium ore bed is prepared by two step spin-coating steps；Two step spin coatings
When, 10s is rotated with 1000rpm speed respectively and 20s is rotated with 6000rpm speed；In the last 5s of second of spin coating process
Chlorobenzene anti-solvent is added dropwise；Then, substrate is dried into 1h under the conditions of 100 DEG C, calcium titanium ore bed is made；
(5) hole transmission layer is prepared
It is 15mg/mL solution that chemical compounds I, which is added in chlorobenzene, and is configured to concentration, then by solution with the speed spin coating of 6000rpm
30s is deposited on calcium titanium ore bed；
Chemical compounds I is replaced with into any one in compound ii, compound III, compounds Ⅳ or compound V, can be made
The hole transmission layer of corresponding ingredient；
(6) it is placed in vacuum evaporation room, metal electrode is deposited to hole transport layer surface by vacuum vapour deposition, perovskite is made
Solar cell device.
6. according to the method described in claim 5, it is characterized by: bis- (levulinic ketone group) diisopropyls of the step (2)
In the butanol solution of titanate esters, the volume ratio of bis- (levulinic ketone group) diisopropyl titanate esters and butanol is 1: 10.
7. according to the method described in claim 5, it is characterized by: in the step (3), TiO2The mass ratio of slurry and ethyl alcohol
It is 1: 6.
8. according to the method described in claim 5, it is characterized by: in the precursor solution in step (4), FAI concentration is
0.95M, PbI2Concentration is 1M, and MABr concentration is 0.2M, PbBr2Concentration is 0.2M, and CsI concentration is 0.06M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811304172.2A CN109503457B (en) | 2018-11-03 | 2018-11-03 | Dinaphtho heterocyclic small molecule hole transport material, synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811304172.2A CN109503457B (en) | 2018-11-03 | 2018-11-03 | Dinaphtho heterocyclic small molecule hole transport material, synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109503457A true CN109503457A (en) | 2019-03-22 |
| CN109503457B CN109503457B (en) | 2021-02-02 |
Family
ID=65747462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811304172.2A Active CN109503457B (en) | 2018-11-03 | 2018-11-03 | Dinaphtho heterocyclic small molecule hole transport material, synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109503457B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903296A (en) * | 2019-11-28 | 2020-03-24 | 北京燕化集联光电技术有限公司 | OLED material and application thereof in device |
| CN110903302A (en) * | 2019-11-28 | 2020-03-24 | 北京燕化集联光电技术有限公司 | Xanthene OLED material and synthetic method and application thereof |
| CN111004253A (en) * | 2019-11-28 | 2020-04-14 | 北京燕化集联光电技术有限公司 | OLED material and application thereof |
| CN111004249A (en) * | 2019-11-28 | 2020-04-14 | 北京燕化集联光电技术有限公司 | Novel OLED material and application thereof |
| CN111039953A (en) * | 2019-11-28 | 2020-04-21 | 北京燕化集联光电技术有限公司 | Xanthene organic material and application thereof in devices |
| CN111116602A (en) * | 2019-11-28 | 2020-05-08 | 北京燕化集联光电技术有限公司 | Novel OLED material and application thereof in organic electroluminescent device |
| CN111153894A (en) * | 2020-01-05 | 2020-05-15 | 浙江大学 | Arylamine compound and application thereof in photoelectric device |
| CN113135925A (en) * | 2021-04-14 | 2021-07-20 | 浙江大学 | Aza-spiroalkene micromolecule perovskite solar cell hole transport material and preparation method thereof |
| CN113501894A (en) * | 2021-07-05 | 2021-10-15 | 福州大学 | Methacrylate copolymer based on photocatalysis and medical optical polymer |
| CN113801057A (en) * | 2021-08-13 | 2021-12-17 | 浙江大学 | chrysene radical aza [7] spiroalkene compound, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101490208A (en) * | 2006-07-28 | 2009-07-22 | 默克专利有限公司 | Novel materials for organic electroluminescent devices |
| CN106588748A (en) * | 2016-12-05 | 2017-04-26 | 中国科学院长春应用化学研究所 | Phenanthrocarbazole compound, preparation method therefor, application of phenanthrocarbazole compound and perovskite solar cells |
| CN106957381A (en) * | 2017-05-12 | 2017-07-18 | 南京工业大学 | Design, synthesis and the application of the hole mobile material of one perovskite-like solar cell |
-
2018
- 2018-11-03 CN CN201811304172.2A patent/CN109503457B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101490208A (en) * | 2006-07-28 | 2009-07-22 | 默克专利有限公司 | Novel materials for organic electroluminescent devices |
| CN106588748A (en) * | 2016-12-05 | 2017-04-26 | 中国科学院长春应用化学研究所 | Phenanthrocarbazole compound, preparation method therefor, application of phenanthrocarbazole compound and perovskite solar cells |
| CN106957381A (en) * | 2017-05-12 | 2017-07-18 | 南京工业大学 | Design, synthesis and the application of the hole mobile material of one perovskite-like solar cell |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903296A (en) * | 2019-11-28 | 2020-03-24 | 北京燕化集联光电技术有限公司 | OLED material and application thereof in device |
| CN110903302A (en) * | 2019-11-28 | 2020-03-24 | 北京燕化集联光电技术有限公司 | Xanthene OLED material and synthetic method and application thereof |
| CN111004253A (en) * | 2019-11-28 | 2020-04-14 | 北京燕化集联光电技术有限公司 | OLED material and application thereof |
| CN111004249A (en) * | 2019-11-28 | 2020-04-14 | 北京燕化集联光电技术有限公司 | Novel OLED material and application thereof |
| CN111039953A (en) * | 2019-11-28 | 2020-04-21 | 北京燕化集联光电技术有限公司 | Xanthene organic material and application thereof in devices |
| CN111116602A (en) * | 2019-11-28 | 2020-05-08 | 北京燕化集联光电技术有限公司 | Novel OLED material and application thereof in organic electroluminescent device |
| CN110903296B (en) * | 2019-11-28 | 2021-08-20 | 北京燕化集联光电技术有限公司 | OLED material and application thereof in device |
| CN111004249B (en) * | 2019-11-28 | 2021-08-20 | 北京燕化集联光电技术有限公司 | OLED material and application thereof |
| CN111116602B (en) * | 2019-11-28 | 2021-05-14 | 北京燕化集联光电技术有限公司 | OLED material and application thereof in organic electroluminescent device |
| CN111004253B (en) * | 2019-11-28 | 2021-06-29 | 北京燕化集联光电技术有限公司 | OLED material and application thereof |
| WO2021135261A1 (en) * | 2020-01-05 | 2021-07-08 | 浙江大学 | Aromatic amine compound and application thereof in optoelectronic device |
| CN111153894B (en) * | 2020-01-05 | 2021-05-14 | 浙江大学 | Arylamine compound and application thereof in photoelectric device |
| CN111153894A (en) * | 2020-01-05 | 2020-05-15 | 浙江大学 | Arylamine compound and application thereof in photoelectric device |
| JP2022518662A (en) * | 2020-01-05 | 2022-03-16 | 浙江大学 | Its use in aromatic amine compounds and optoelectronic devices |
| JP7265738B2 (en) | 2020-01-05 | 2023-04-27 | 浙江大学 | Aromatic amine compounds and their use in photoelectric devices |
| CN113135925A (en) * | 2021-04-14 | 2021-07-20 | 浙江大学 | Aza-spiroalkene micromolecule perovskite solar cell hole transport material and preparation method thereof |
| CN113501894A (en) * | 2021-07-05 | 2021-10-15 | 福州大学 | Methacrylate copolymer based on photocatalysis and medical optical polymer |
| CN113501894B (en) * | 2021-07-05 | 2022-07-26 | 福州大学 | Methacrylate copolymer based on photocatalysis and medical optical polymer |
| CN113801057A (en) * | 2021-08-13 | 2021-12-17 | 浙江大学 | chrysene radical aza [7] spiroalkene compound, preparation method and application |
| CN113801057B (en) * | 2021-08-13 | 2023-04-18 | 浙江大学 | chrysene-base aza [7] spiroalkene compound, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109503457B (en) | 2021-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109503457A (en) | Dinaphtho heterocycle small molecule hole transport material, synthetic method and its application | |
| CN109037398B (en) | Preparation method of cesium tin iodine film and photovoltaic device based on cesium tin iodine film | |
| KR101711315B1 (en) | Metal-complex dye, photoelectric conversion element, dye-sensitized solar cell, and dye solution containing metal-complex dye | |
| CN102753598B (en) | Copolymer comprising anthracene and benzoselenadiazole, preparing method and uses thereof | |
| KR101194735B1 (en) | Ruthenium Complex | |
| KR101982944B1 (en) | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution, and terpyridine compound or esterification product thereof | |
| CN103554957A (en) | Triphenylamine-thiophene organic dyestuff as well as preparation method and application thereof | |
| CN112979611A (en) | Bowl alkenyl perovskite solar cell hole transport layer material and preparation method and application thereof | |
| JP2010100847A (en) | Ruthenium complex and photoelectric component using the same | |
| KR101982945B1 (en) | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution, and terpyridine compound or esterification product thereof | |
| CN112521403B (en) | Seven-membered fused ring compound and organic photovoltaic cell | |
| KR101947886B1 (en) | Photoelectric conversion element, dye-sensitized solar cell, metal-complex pigment, and pigment solution | |
| KR101760492B1 (en) | Novel compounds, method of preparation thereof and organic solar cell comprising the same | |
| CN113801057B (en) | chrysene-base aza [7] spiroalkene compound, preparation method and application | |
| CN114621276A (en) | Benzothiadiazole boron-nitrogen derivative and application thereof | |
| CN109836369B (en) | Spiroindene hole transport small molecule and application thereof in perovskite solar cell | |
| CN113336772A (en) | Hole transport material and synthesis method and application thereof | |
| CN116621848B (en) | Perylene-based fused ring compound, preparation method and application | |
| CN102863812B (en) | Organic dye and dye-sensitized solar cell | |
| EP2700640A1 (en) | Azulenocyanine compounds, method of making the same, and their use as semiconductor and absorber for organic photovoltaics | |
| JP6410669B2 (en) | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye and dye solution | |
| WO2012118346A2 (en) | Cobalt-based compound for solar cell | |
| CN116731074A (en) | Self-assembled hole selection material containing large pi symmetrical nitrogen heterocyclic element and application thereof | |
| KR101205922B1 (en) | Ruthenium Complex Compound And Dye-sensitized Solar Cells Comprising The Same | |
| CN102532032A (en) | Benzo nitrogen-containing heterocyclic compound and preparation method, intermediate 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |