CN105593206B - 空穴传输材料 - Google Patents
空穴传输材料 Download PDFInfo
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- CN105593206B CN105593206B CN201480054535.5A CN201480054535A CN105593206B CN 105593206 B CN105593206 B CN 105593206B CN 201480054535 A CN201480054535 A CN 201480054535A CN 105593206 B CN105593206 B CN 105593206B
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000000975 dye Substances 0.000 claims description 22
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- 230000001235 sensitizing effect Effects 0.000 claims description 4
- 238000005401 electroluminescence Methods 0.000 claims description 3
- 239000012212 insulator Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- -1 methoxyl group Chemical group 0.000 abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 239000000203 mixture Substances 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 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 10
- 239000000376 reactant Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
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- 238000009835 boiling Methods 0.000 description 6
- 239000012925 reference material Substances 0.000 description 6
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- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
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- 229910052744 lithium Inorganic materials 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
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- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
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- 150000002466 imines Chemical class 0.000 description 3
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- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 101100205030 Caenorhabditis elegans hars-1 gene Proteins 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000002012 dioxanes Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000001972 liquid chromatography-electrospray ionisation mass spectrometry Methods 0.000 description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
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- 239000012265 solid product Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 description 1
- HXSDFCKKOUCOIZ-XCSHDWRRSA-N 12-[(5E)-5-[3-(carboxymethyl)-5-[[4-[4-(2,2-diphenylethenyl)phenyl]-2,3,3a,8b-tetrahydro-1H-cyclopenta[b]indol-7-yl]methylidene]-4-oxo-1,3-thiazolidin-2-ylidene]-4-oxo-2-sulfanylidene-1,3-thiazolidin-3-yl]dodecanoic acid Chemical compound OC(=O)CCCCCCCCCCCN1C(=S)S\C(C1=O)=c1\sc(=Cc2ccc3N(C4CCCC4c3c2)c2ccc(C=C(c3ccccc3)c3ccccc3)cc2)c(=O)n1CC(O)=O HXSDFCKKOUCOIZ-XCSHDWRRSA-N 0.000 description 1
- VMISXESAJBVFNH-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid;ruthenium(2+);diisothiocyanate Chemical compound [Ru+2].[N-]=C=S.[N-]=C=S.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 VMISXESAJBVFNH-UHFFFAOYSA-N 0.000 description 1
- OZFUEQNYOBIXTB-SJIUXOFISA-N 2-[(2e,5z)-5-[[4-[4-(2,2-diphenylethenyl)phenyl]-2,3,3a,8b-tetrahydro-1h-cyclopenta[b]indol-7-yl]methylidene]-2-(3-ethyl-4-oxo-2-sulfanylidene-1,3-thiazolidin-5-ylidene)-4-oxo-1,3-thiazolidin-3-yl]acetic acid Chemical compound O=C1N(CC)C(=S)S\C1=C(\S\1)N(CC(O)=O)C(=O)C/1=C/C1=CC=C(N(C2C3CCC2)C=2C=CC(C=C(C=4C=CC=CC=4)C=4C=CC=CC=4)=CC=2)C3=C1 OZFUEQNYOBIXTB-SJIUXOFISA-N 0.000 description 1
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- FRYSEKUUHUUJPX-UHFFFAOYSA-N 2-pyridin-2-ylpyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=CC=2)=C1 FRYSEKUUHUUJPX-UHFFFAOYSA-N 0.000 description 1
- BJWNRQMDECXKTE-UHFFFAOYSA-N 3,3-dimethylbutylphosphonic acid Chemical class CC(C)(C)CCP(O)(O)=O BJWNRQMDECXKTE-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-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
- VHJFWJXYEWHCGD-UHFFFAOYSA-N 4-nonyl-2-(4-nonylpyridin-2-yl)pyridine Chemical group CCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCC)C=2)=C1 VHJFWJXYEWHCGD-UHFFFAOYSA-N 0.000 description 1
- 241001385733 Aesculus indica Species 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 229910019394 NaRu Inorganic materials 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- JTDNNCYXCFHBGG-UHFFFAOYSA-L Tin(II) iodide Inorganic materials I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- 150000001500 aryl chlorides Chemical class 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
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- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004246 ligand exchange chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- WLPHVBCUECCENX-UHFFFAOYSA-N lithium;methyl hydrogen sulfate Chemical compound [Li].COS(O)(=O)=O WLPHVBCUECCENX-UHFFFAOYSA-N 0.000 description 1
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical class COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- PVVPEBXWAUQMLW-UHFFFAOYSA-N pyridine;ruthenium(2+) Chemical compound [Ru+2].C1=CC=NC=C1 PVVPEBXWAUQMLW-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及2,2’,7,7’‑四‑(N,N’‑二‑4‑甲氧基‑3‑甲基苯胺)‑9,9’‑螺双芴，其制备方法，及其作为用于电子或光电器件，特别是固态染料敏化太阳能电池的空穴传输材料。
Description
本发明涉及2,2’,7,7’-四-(N,N’-二-4-甲氧基-3-甲基苯胺)-9,9’-螺双芴，其制备方法，以及其作为用于电子或光电器件，特别是用于固态染料敏化太阳能电池或者含钙钛矿的太阳能电池的空穴传输材料的用途。
染料敏化太阳能电池或者含钙钛矿的太阳能电池的应用是非常有前景的技术，其通过太阳光辐射产生光电流。液体电解质染料敏化太阳能电池的能量转换效率达到11％以上。然而，液体电解质基太阳能电池现有任务之一是避免泄露问题。因此，研究者们采用固态空穴导体或换言之空穴传输材料(HTMs)来代替液体电解质。直到如今，空穴传输材料2,2’,7,7’-四-(N,N’-二-4-甲氧基苯胺)-9,9’-螺双芴(spiro-OMeTAD)一直被选为用于固态染料敏化太阳能电池(SDDSC)的基准HTM(Nature,1998,395,585)。然而，spiro-OMeTAD具有相对较低的载流子迁移率，在10-4cm2/Vs量级。
除spiro-OMeTAD外，JP 2011-258328也介绍了一些空穴传输材料，特别是化合物39，2,2’,7,7’-四-(N,N’-二-4-甲氧基-3,5-二甲基苯胺)-9,9’-螺双芴。
此外，需要解决的一个重要问题是HTM的溶解性，因为HTM必须可从溶液中加工，应有效地填充半导体的孔隙以及应形成光滑膜。
因此，仍然需要空穴传输材料以进一步优化电子或者光电器件的性能，特别是优化sDSSCs。
因此，本发明要解决的问题是提供一种用于电子或光电器件中的具有改进性能的替代空穴传输材料。
现已惊奇地发现，式(I)化合物，2,2’,7,7’-四-(N,N’-二-4-甲氧基-3-甲基苯胺)-9,9’-螺双芴，是一种具有合意性能的空穴传输材料。
因此本发明涉及式(I)化合物
这种空穴传输材料相对于现有技术分子spiro-OMeTAD和2,2’,7,7’-四-(N,N’-二-4-甲氧基-3,5-二甲基苯胺)-9,9’-螺双芴具有更好的溶解性。惊奇地是，尽管在结构中引入8个非极性甲基基团得到式(I)化合物，但其溶解性好于spiro-OMeTAD。本发明的空穴传输材料相对于两种参考材料均具有更好的空穴迁移率。
因此，如实验部分描述的包含式(I)化合物的固态DSSC的电池性能好于参考物质2,2’,7,7’-四-(N,N’-二-4-甲氧基-3,5-二甲基苯胺)-9,9’-螺双芴的sDSSC的性能，与含有spiro-OMeTAD的sDSSC的性能相当。
本发明进一步涉及式(I)化合物的制备方法，包括使2,2’,7,7’-四溴-9,9’-螺双芴与双(4-甲氧基-3-甲基苯胺)以Buchwald-Hartwig(布赫瓦尔德-哈特维希)氨基化进行反应。
起始原料2,2’,7,7’-四溴-9,9’-螺双芴是市售的，如可购自TCI或者Sigma-Aldrich。
本发明进一步涉及起始材料双(4-甲氧基-3-甲基苯胺)。
双(4-甲氧基-3-甲基苯胺)可通过5-溴-2-甲氧基-1,3-二甲基苯与4-甲氧基-3,5-二甲基苯胺反应进行合成。反应条件属于本领域中已广为人知的Buchwald-Hartwig氨基化反应条件。
本发明进一步涉及双(4-甲氧基-3-甲基苯胺)的制备方法，包括使5-溴-2-甲氧基-1,3-二甲基苯与4-甲氧基-3,5-二甲基苯胺以Buchwald-Hartwig氨基化进行反应。
合成双(4-甲氧基-3-甲基苯胺)的优选反应条件是使用叔丁醇钠作为碱，使用乙酸钯(II)作为Pd-催化剂中的钯(0)的来源，使用1,1’-双(二苯基膦基)二茂铁(DPPF)作为配体。Buchwald-Hartwig反应优选在有机溶剂存在下进行，如甲苯、苯、二噁烷、四氢呋喃、二甲基甲酰胺或者二甲氧基乙烷。优选使用甲苯作为溶剂。
反应温度通常为室温至120℃。
另外，式(I)化合物的合成方法也是Buchwald-Hartwig氨基化反应。Buchwald-Hartwig氨基化反应条件是本领域广为人知的。合成式(I)化合物的优选反应条件是：使用叔丁醇钠，使用乙酸钯(II)作为Pd-催化剂中钯(0)的来源，使用2-二环己基膦-2’,6’-二甲氧基联苯(SPhos)作为配体。
Sphos-Pd-络合物在包括芳基氯或者芳基溴的Buchwald-Hartwig氨基化反应中具有高活性。Buchwald-Hartwig反应优选在有机溶剂存在下进行，如甲苯、苯、二噁烷、四氢呋喃、二甲基甲酰胺或者二甲氧基乙烷。优选使用甲苯作为溶剂，反应温度通常为室温至120℃，优选120℃。
优选地，所有Buchwald-Hartwig氨基化在非反应性气体如氮气(N2)存在下进行。
通过上述方法制备的式(I)化合物可通过本领域技术人员熟知的多种提纯方法进行提纯，例如层析法或者重结晶法。
本发明进一步涉及一种制剂，其包含式(I)化合物和至少一种溶剂。
该制剂可以包括或者包含所述必需组分或者任选组分，实质上由所述必需组分或者任选组分组成或者由所述必需组分或者任选组分组成。可用于制剂中的所有化合物或者组分是已知和市售的，或者可通过已知方法合成。
除式(I)化合物之外，这里的制剂包括适于所用施涂方法的有机溶剂。合适的方法是浸渍、滴加、刮刀、旋涂、刷涂、喷涂或者辊涂机。这些技术是本领域技术人员所公知的。优选的方法是旋涂或者浸渍。特别优选的方法是旋涂。在大多数情况下，旋涂的溶剂具有高沸点。
根据本发明使用的合适溶剂是例如氯苯、四氢呋喃、环氧丁烷、氯仿、环己酮、丙酮、醇如甲醇或乙醇、二甲基甲酰胺、乙腈、二甲氧基乙烷、六甲基磷酰三胺、1,2-二氯苯或者其混合物。优选的溶剂是氯苯。
本发明还涉及这种类型制剂的制备方法，其特征在于式(I)化合物与至少一种溶剂和任选的其他化合物混合和/或溶解。
制剂中式(I)化合物的典型摩尔浓度范围为0.08-0.5M，优选0.1-0.2M。制剂中特别优选的浓度为0.17M。根据本发明的目的，摩尔浓度是指25℃下的浓度。
另外，本发明的制剂可包含一种或者更多种其他空穴传输材料。
合适的其他空穴传输材料是本领域公知的。优选用于组合的空穴传输材料是spiro-OMeTAD，2,2’,7,7’-四(N,N’-二-4-甲氧基-3,5-二甲基苯胺)-9,9’-螺双芴，三(p-茴香基)胺，N,N,N’,N’-四(4-甲氧基苯基)-1,1’-联苯-4,4’二胺，2,7-双[N,N-双(4-甲氧基-苯基)氨基]-9,9’-螺双芴，聚(3-己基噻吩)(P3HT)，聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(PEDOT:PSS)，聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PATT)，NiO和V2O5。
另外，本发明的制剂可包含至少一种锂盐。
合适的锂盐是双(三氟甲基磺酰)亚胺锂，三(五氟乙基)三氟磷酸锂，二氰氨基锂，甲基硫酸锂，三氟甲磺酸锂，四氰硼酸锂，二氰氨基锂，三氰甲基锂，硫氰酸锂，氯化锂，溴化锂，碘化锂，六氟磷酸锂，四氟硼酸锂，高氯酸锂，六氟锑酸锂，六氟砷酸锂或者两种或更多种的组合。优选的锂盐为双(三氟甲基磺酰)亚胺锂。
优选地，其包含1mM-30mM，优选8-15mM的锂盐。
另外，本发明的制剂可以包含至少一种其他添加剂。
合适的添加剂为吡啶化合物如叔丁基吡啶，如WO2013/026563的权利要求1-15和第15-17页公开的咪唑类化合物，或者聚合物添加剂如聚(4-乙烯基吡啶)或者其与例如乙烯基苯乙烯或者甲基丙烯酸烷基酯的共聚物。优选的吡啶化合物是叔丁基吡啶。优选地，制剂包含0.01M-0.3M，优选0.08-0.15M的添加剂。
在一个优选的实施方案中，室温下式(I)化合物：锂盐：吡啶化合物添加剂的摩尔比为10:1:10。
本发明的一种优选制剂是包含如上所述或者如上所述优选的式(I)化合物，至少一种溶剂，锂盐和吡啶化合物的制剂。
锂盐的使用性描述于Phys.Chem.,Chem.Phys,2013,15,1572-2579。
吡啶化合物的使用性描述于Sol.Energy Mater.&Solar Cells,2007,91,424-426。
另外，如上所述的本发明的制剂可包含p-掺杂剂，例如N(PhBr)3SbCl6(其中Ph是苯基)，V2O5，如Phys.Chem,Chem.,Phys,2012,14,11689-11694中所描述的F4-TCNQ(四氟-四氰基醌二甲烷)，HAT-CN(1,4,5,8,9,11-六氮杂苯并菲-六甲腈)或者如Chem.Mater.,2013,25,2986-2990或J.Am.Chem.Soc.,2011,133,18042中所描述的Co络合物盐。
如上所述的式(I)化合物为空穴传输材料，并且因此也可用于电子或者光电器件中。
因此本发明还涉及式(I)化合物在电子或者光电器件中的用途。
因此本发明还涉及包含式(I)化合物的电子或者光电器件。
这里的电子器件是指这样的器件，其包括至少一层，该层含有至少一种有机化合物。然而，器件还可以包含无机材料或者还可以包含完全由无机材料构建的层。
电子或者光电器件优选选自下组：有机电致发光器件(OLEDs)、有机集成电路(O-ICs)、有机场效应晶体管(O-FETs)、有机薄膜晶体管(O-TFTs)、有机发光晶体管(O-LETs)、太阳能电池、有机光检测器、有机光感受器、有机场淬灭器件(organic field-quenchdevices,O-FQDs)、发光电化学电池(LECs)、有机激光二极管(O-lasers)、有机等离子体发射器件(D.M.Koller et al.,Nature Photonics 2008,1-4)、电子照相器件以及波转换器。
式(I)化合物是例如波转换器的波转换层的一部分。
电子器件优选为有机电致发光器件(OLED)或者有机发光电化学电池(OLEC)。
光电器件优选是固态染料敏化太阳能电池或者含钙钛矿的太阳能电池。光电器件特别优选是固态染料敏化太阳能电池。
器件的进一步特征是式(I)化合物作为空穴传输材料使用。
本发明进一步涉及包含式(I)化合物的电荷传输层。
本发明的电荷传输层可包含上述添加剂或者如前所述的其他HTMs。
本发明的电荷传输层可包含有机粘结剂，优选聚合物粘结剂。
根据本发明使用的合适粘结剂是聚氧乙烯(PEO)，聚偏氟乙烯(PVDF)，聚碳酸酯，聚丙烯酸酯，聚丙烯酸甲酯，聚甲基丙烯酸甲酯，聚苯乙烯，聚氯乙烯或者聚硅氧烷。
本发明的电荷传输层优选为光敏纳米微粒层，包含敏化染料(sensitizing dye)或者钙钛矿和式(I)化合物。
对于敏化染料的选择没有限制，只要LUMO能态略微高于待敏化的光电极的传导带缘(conduction bandedge)即可。染料的例子公开于Nanoenergy,de Souza,FlavioLeandro,Leite,Edson Roberto(Eds.),Springer,ISBN 978-3-642-31736-1,第58-74页，或者如US 8,383,553公开的黑色染料。
优选的染料是有机染料，例如J.Power Sources,2012,214,113-118中描述的CYC-B11，MK-1、MK-2或MK-3(其结构描述于N.Koumura et al,J.Am.Chem.Soc.Vol 128,no.44,2006,14256-14257的图1)，WO 2012/001033第4页描述的D29，WO 2012/001033第4页描述的D35，D102(CAS no.652145-28-3),D-149(CAS no.786643-20-7)，D205(CAS no.936336-21-9),D358(CAS no.1207638-53-6)，T.Bessho et al,Angew.Chem.Int.Ed.Vol 49,37,6646-6649,2010中描述的YD-2，Y123(CAS no.1312465-92-1)，联吡啶-钌染料如N3(CASno.141460-19-7)，N719(CAS no.207347-46-4)，Z907(CAS no.502693-09-6)，C101(CASno.1048964-93-7)，C106(CAS no.1152310-69-4)，K19(CAS no.847665-45-6)，HRS-1(CASno.906061-30-1，如K.J.Jiang et al,Chem.Comm.2460,2006中所述)或者三联吡啶-钌染料如N749(CAS no.359415-47-7)。
D205的结构是
D358的结构是
特别优选的染料是Z907或者Z907Na，两者均是两亲性钌敏化剂，D29，D35，Y123，C106，D358或者HRS-1。染料Z907Na是指NaRu(2,2’-联吡啶-4-甲酸-4’-甲酸盐)(4,4’-二壬基-2,2’-联吡啶)(NCS)2。
特别优选的染料是Z907。
钙钛矿材料的选择没有限制。钙钛矿材料充当光吸收结构部分是已知的，但其也可在功能上描述为充当空穴传输材料或者半导体。
因此，本发明的器件中包含的钙钛矿材料可以是电荷传输层的一部分，但也可以是另外层的一部分或者器件内的支架(scaffold)。
合适的钙钛矿材料是CsSnI3，CH3NH3PbI2Cl，CH3NH3PbI3，CH3NH3Pb(I1-xBrx)3，CH3NH3SnI2Cl，CH3NH3SnI3或CH3NH3Sn(I1-xBrx)3，其中x各自独立地如下所定义：(0<x≤1)。更概括地，合适的钙钛矿材料可包括对应于式Xa(3-x)Xb(x)的二卤化合物，其中Xa和Xb各自独立地选自Cl、Br或者I，x大于0且小于3。
合适的钙钛矿材料还公开于WO 2013/171517的权利要求52-71以及权利要求72-79，其通过引用完全引入本文。这些材料定义为混合阴离子钙钛矿，其包含两种或者更多种不同的选自卤素阴离子和硫系阴离子的阴离子。优选的钙钛矿材料公开于第18页，第5-17行。如上所述，钙钛矿通常选自CH3NH3PbBrI2，CH3NH3PbBrCl2，CH3NH3PbIBr2，CH3NH3PbICl2，CH3NH3SnF2Br，CH3NH3SnF2I和(H2N＝CH-NH2)PbI3zBr3(1-z)，其中z大于0且小于1。
如前所述的本发明的电荷传输层或者如前所述或者如下所述的本发明的器件还可以包含绝缘体，如氧化铝，如Michael M.Lee et al,Science,338,643,2012中所述。
本发明的电荷传输层或者如前所述或者如下所述的本发明的器件还可以包含半导体氧化物纳米微粒。本发明的电荷传输层或者本发明的器件优选包含半导体氧化物纳米微粒。
根据本发明的一个优选实施方案，半导体基于选自下组的材料：Si、TiO2、SnO2、Fe2O3、WO3、ZnO、Nb2O5、CdS、ZnS、PbS、Bi2S3、CdSe、GaP、InP、GaAs、CdTe、CuInS2和/或CuInSe2。优选地，半导体包括中孔表面，从而增大了任选被敏化染料或者钙钛矿材料覆盖以及与空穴传输材料接触的表面。优选地，半导体氧化物纳米微粒是二氧化钛纳米微粒。优选地，半导体氧化物是中孔的。
优选地，如前所述的本发明的电荷传输层，任选地与TiO2致密层一起，存在于玻璃载体或者塑料或者金属箔上。优选地，载体是导电的。
本发明进一步涉及电子器件或者光电器件，其包括如前所述的或者如前所述优选的电荷传输层。优选地，本发明还涉及固态染料敏化太阳能电池，其包括如前所述的或者如前所述优选的电荷传输层。
进一步包括混合卤化物钙钛矿的本发明合适器件结构描述于WO2013/171517，权利要求52-71和权利要求72-79，其内容通过引用完全并入本文。
进一步包括介电支架以及钙钛矿材料的本发明合适器件结构描述于WO2013/171518的权利要求1-90，或者WO2013/171520的权利要求1-94，其内容通过引用完全并入本文。
进一步包括半导体和钙钛矿材料的本发明合适器件结构描述于WO2014/020499，权利要求1和3-14，其内容通过引用完全并入本文。其中所述的增加表面的支架结构包括纳米微粒，其施加和/或固定于载体层上，如多孔TiO2。
包括平面异质结的本发明合适器件结构描述于WO 2014/045021，权利要求1-39，其内容通过引用完全并入本文。这类器件的特征在于具有沉积在n型(电子传导)和p型(空穴传导)层之间的光吸收或光发射钙钛矿薄膜。优选地，薄膜是密实薄膜。
另外，本发明涉及制备如前所述的或者如前所述优选的电化学器件和/或光电器件的方法，该方法包括如下步骤：
-提供第一和第二电极，
-提供如前所述的本发明的电荷传输层。
对于第一和第二电极的选择没有限制。基底可以是刚性或者柔性的。
本发明的一个优选实施方案是固态染料敏化太阳能电池，其包括涂覆有F掺杂的SnO2的玻璃基底，致密的TiO2层，如前所述的或者如前所述优选的本发明电荷传输层和对电极。
优选地，对电极是金电极，银电极或者铂电极。特别优选地，对电极是金或者银电极。
本发明还涉及模块，其包括一个如前所述的或者如前所述优选的本发明的器件。
本发明还涉及模块，其包括多个如前所述的或者如前所述优选的本发明的器件。
以下通过实施例对本发明进行说明，但并不限制其范围。即使没有进一步说明，也可认为本领域技术人员能够在最宽范围内利用上述描述。因此优选的实施方案以及实施例应仅被视为描述性公开内容而绝非以任何方式进行限制。
实施例
实施例1：合成2,2’,7,7’-四-(N,N’-二-4-甲氧基-3-甲基苯胺)-9,9’-螺双芴
步骤1：合成双(4-甲氧基-3-甲基苯胺)
将4-溴-1-甲氧基-2-甲基苯(3.134mg，15.6mmol)，叔丁醇钠(3.053g，32mmol)，乙酸钯(II)(69mg，0.3mmol)，1,1’-双(二苯基膦)二茂铁(DPPF)(169mg，0.3mmol)在带冷凝器的四口烧瓶中溶解于甲苯(10ml)中。反应混合物在N2气流下搅拌5分钟，然后加入4-甲氧基-3-甲基苯基苯胺(2.064g，15.0mmol)和40mL甲苯。将混合物加热到120℃保持21h。反应后，过滤反应混合物。通过旋转蒸发仪浓缩和通过硅胶快速柱层析(己烷/EtOAc 2％->20％)提纯后，得到橙色粘性油产物。该油用己烷热重结晶，得到双(4-甲氧基-3-甲基苯)胺白色固体[2.725g，10.6mmol，产率70.4％]。
C16H19NO2，MW 257.33，精确值MS 257，GC-MS 257[M]+)。
步骤2：合成2,2’,7,7’-四-(N,N’-二-4-甲氧基-3-甲基苯胺)-9,9’-螺双芴
将2,2’,7,7’-四溴-9,9’-螺双芴(639mg，1.01mmol)，叔丁醇钠(608g，6.33mmol)，乙酸钯(II)(29mg，0.13mmol)，2-二环己基膦-2’,6’-二甲氧基联苯(SPhos)(41mg，0.10mmol)在带冷凝器的四口烧瓶中溶解于甲苯(10ml)中。反应混合物在N2气流下搅拌5分钟，然后加入根据步骤1制备的双(4-甲氧基-3-甲基苯胺)(1.253g，4.87mmol)和甲苯(20mL)。将混合物加热到120℃保持16h。反应后，过滤反应混合物。通过旋转蒸发仪浓缩和通过硅胶快速柱层析(己烷/EtOAc 5％->40％)提纯后，得到米色非晶固体产物[1.082g，0.81mmol，产率80.0％]。
C89H84N4O8，MW 1337.64，精确值MS 1336，LC-ESI-MS 1337.7[M+H]+)。
实施例2：合成参考材料spiro-OMeTAD
将2,2’7,7’-四溴-9,9’-螺双芴(1.896mg，3.0mmol)，叔丁醇钠(1.822g，19mmol)，乙酸钯(II)(1.6mg，0.01mmol)，2-二环己基膦-2’,6’-二甲氧基联苯(SPhos)(6.8mg，0.02mmol)在带冷凝器的四口烧瓶中溶解于甲苯(10mL)中。反应混合物在N2气流下搅拌5分钟，然后加入双(4-甲氧基苯胺)(3.620g，15.7mmol)和甲苯(25mL)。将混合物加热到120℃保持70h。反应后，将反应混合物过滤和浓缩。使用二氯甲烷和甲醇将产物重结晶。实施例3：合成参考材料2,2’7,7’-四(N,N’-二-4-甲氧基-3,6-二甲基苯胺)-9,9’-螺双芴
步骤1：合成双(4-甲氧基-3,6-二甲基苯胺)
将5-溴-2-甲氧基-1,3-二甲基苯(4.179mg，21.9mmol)，叔丁醇钠(4.468g，46.5mmol)，乙酸钯(II)(93mg，0.4mmol)，1,1’-双(二苯基膦)二茂铁(DPPF)(220mg，0.4mmol)在带冷凝器的四口烧瓶中溶解于甲苯(20mL)中。反应混合物在N2气流下搅拌5分钟，然后加入4-甲氧基-3,5-二甲基苯胺(3.032g，20.0mmol)和60mL的甲苯。将混合物加热到120℃保持20h。反应后，将反应混合物过滤。通过旋转蒸发仪浓缩和通过硅胶快速柱层析(己烷/EtOAc 2％->20％)提纯后，得到橙色粘性油产物。该油用己烷热重结晶，得到双(4-甲氧基-3,5-甲基苯基)胺白色固体[2.961g，10.37mmol，产率51.7％]。
C18H23NO2，MW 285.38，精确值MS 285，GC-MS 285.1[M]+UV max 288nm。
步骤2：合成2,2’7,7’-四(N,N’-二-4-甲氧基-3,6-二甲基苯胺)-9,9’-螺双芴
将2,2’7,7’-四溴-9,9’-螺双芴(316mg，0.5mmol)、叔丁醇钠(629g，6.55mmol)、乙酸钯(II)(12mg，0.05mmol)、2-二环己基膦-2’,6’-二甲氧基联苯(SPhos)(22mg，0.05mmol)在带冷凝器的四口烧瓶中溶解于甲苯(5mL)中。反应混合物在N2气流下搅拌5分钟，然后加入双(4-甲氧基-3,5-二甲基苯胺)(C-1)(316g，1.11mmol)和甲苯(25mL)。将混合物加热到120℃保持50min。反应后，将反应混合物过滤。通过旋转蒸发仪浓缩和通过硅胶快速柱层析(己烷/EtOAc 5％->80％)提纯后，得到米色非晶固体产物[190mg，0.13mmol，产率26.6％]。
C97H100N4O8，MW 1449.85，精确值MS 1448，LC-ESI-MS 1449.1[M+H]+)."
实施例A：实施例1、2和3的化合物的溶解性
一般描述
用于旋涂的溶液如下所述在N2手套箱中制备：首先，将20mg的空穴传输材料溶解于95μL的氯苯中。空穴传输材料需要溶解完全。在室温下单独制备双(三氟磺酰)亚胺锂(LiTFSI)和叔丁基吡啶(TBP)的母液，加入到空穴传输体溶液中，设定室温下[空穴传输体]:[LiTFSI]:[TBP]摩尔比＝10:1:10。由此，溶液的最终体积为100μL。
定性评价实施例1、2和3的HTMs的溶解性：
1是指：20mg的HTM无加热下完全溶解
2是指：HTM加热到80℃后溶解
3是指：HTM在加入盐和碱溶液并加热到80℃后溶解
4是指：HTM在加入另外50μL的氯苯并加热到80℃后溶解(最终体积150μL)
结果示于表1：
本发明的空穴传输材料比参考材料具有更好的溶解性。
实施例B：
使用实施例A中所述的溶液，根据Lukas Schmid-Mende and MichaelThin Solid Films,500,2006,296-301制造固态染料敏化太阳能电池。
使用Helmanex和水清洗图案化ITO/ATO基底(20x 20mm)后，通过溶胶-凝胶法制备TiO2密实层，其中在75℃下使用60mM的TiCl4水溶液进行30分钟，进行3次。通过丝网印刷含有30nm粒度的锐钛矿颗粒的TiO2糊(JGC C&C PST-30NRD)，然后在500℃下煅烧30min制造纳米晶体TiO2层。通过溶胶-凝胶法沉积顶层TiO2涂层，其中在75℃下使用60mM的TiCl4水溶液进行30分钟1次，在500℃下煅烧30min。所得TiO2基材通过如下方式敏化：浸渍于0.3mM的两亲性多吡啶钌(II)络合物(即顺式-RuLL’(SCN)2(L＝4,4’-二甲酸-2,2’-联吡啶，L’＝4,4’-二壬基-2,2’-联吡啶，Z907)与0.075mM的双(3,3’-二甲基-丁基)-膦酸(DINHOP)在乙腈：叔丁醇(1:1vol％)的溶液中，然后在冰箱中放置一夜。独立地使用旋涂机涂覆空穴传输材料。将40μL的溶液施加于基底上，等待30sec，然后在2500rpm的旋涂条件下30sec。为了完成器件的制造，在顶部上蒸发200nm的Ag电极。此程序在一个基底上形成两个电池。在没有密封电池的条件下进行性能测量。
利用源表(source meter，Keithley 2400)测量电流-电压特性，在利用太阳模拟器(L11Peccell Technologies)产生的模拟AM 1.5G太阳光100mW cm-2辐射下，使用校准的硅参考电池(Bukou Keiki,BS-520)进行校准的条件下进行测量。太阳能电池以金属孔掩蔽以限定出通常为0.16cm2的活性区域。
本实验中测量的电池结构以及其电流-电压特性总结于表2中。
表2：每个电池的电流-电压特性性能：
结果表明，本发明的式(I)化合物相对于spiro-OMeTAD具有相当的转换率和更好的溶解性。
实施例C：空穴迁移率
对本发明化合物2,2’,7,7’-四-(N,N’-二-4-甲氧基-3-甲基苯胺)-9,9’-螺双芴的空穴迁移率进行测量，测量值与实施例2和实施例3中的参考材料进行比较。
测量电池的结构是：
ITO(200nm)/PEDOT-PSS(150nm)/HTM(400nm)/Au(60nm)。
PEDOT-PSS是指聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)。
采用阻抗光谱法(文献1.H.Martens et al.,Phys.Rev.B,60,R8489(1999),文献2.S.Ishihara,et al.,Proc.ofIDW’09,p1085(2009))用四个电池对每一HTM进行测量。在阻抗测量中，为了从阳极注射空穴，对待测电池施加直流电(dc)。在dc场强度105V/cm下测量空穴迁移率。测量结果示于图1和表3。
表3：
本发明化合物2,2’,7,7’-四-(N,N’z-二-4-甲氧基-3-甲基苯胺)-9,9’-螺双芴的空穴迁移率大于spiro-OMeTAD的空穴迁移率，比参考例3的空穴迁移率高大于一个数量级。图1的结果能够很好地解释表2中所用空穴传输材料的空穴迁移率的结果。
Claims (18)
1.式(I)化合物
2.权利要求1所述化合物的制备方法，包括使2,2’,7,7’-四溴-9,9’-螺双芴与双(4-甲氧基-3-甲基苯胺)以Buchwald-Hartwig氨基化进行反应。
3.根据权利要求2所述的方法，其中反应在100℃-140℃之间的温度进行。
4.包含根据权利要求1所述的式(I)化合物和至少一种溶剂的制剂。
5.根据权利要求1所述的式(I)化合物在电子或者光电器件中的用途。
6.包含根据权利要求1所述的式(I)化合物的电子或者光电器件。
7.根据权利要求6所述的器件，其为有机电致发光器件，有机集成电路，有机场效应晶体管，有机薄膜晶体管，有机发光晶体管，太阳能电池，有机光检测器，有机光感受器，有机场淬灭器件，发光电化学电池或者有机激光二极管，有机等离子体发射器件，电子照相器件或者波转换器。
8.根据权利要求6所述的器件，其为固态染料敏化太阳能电池或者含钙钛矿的太阳能电池。
9.根据权利要求7所述的器件，其为固态染料敏化太阳能电池或者含钙钛矿的太阳能电池。
10.根据权利要求6-9任一项所述的器件，其特征在于式(I)化合物作为空穴传输材料使用。
11.包含根据权利要求1所述的式(I)化合物的电荷传输层。
12.根据权利要求11所述的层，其为包含敏化染料或者钙钛矿和式(I)化合物的光敏纳米微粒层。
13.根据权利要求11所述的层，其进一步包含绝缘体。
14.根据权利要求12所述的层，其进一步包含绝缘体。
15.根据权利要求11-14任一项所述的层，其包含半导体氧化物纳米微粒。
16.根据权利要求8或9所述的器件，其包括根据权利要求11-14任一项所述的层。
17.根据权利要求8或9所述的器件，其包括根据权利要求15所述的层。
18.包括根据权利要求6-10任一项或者权利要求16或17所述的器件的模块。
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| JP2017028027A (ja) * | 2015-07-17 | 2017-02-02 | 積水化学工業株式会社 | 固体接合型光電変換素子および固体接合型光電変換素子用ｐ型半導体層 |
| JP2017028028A (ja) * | 2015-07-17 | 2017-02-02 | 積水化学工業株式会社 | 固体接合型光電変換素子および固体接合型光電変換素子用ｐ型半導体層 |
| EP3133664A1 (en) * | 2015-08-18 | 2017-02-22 | Novaled GmbH | Triaryl amine thick layer doped with metal amides for use as hole injection layer for an organic light-emitting diode (oled) |
| EP3133663B1 (en) * | 2015-08-18 | 2022-06-15 | Novaled GmbH | Metal amides for use as hole injection layer for an organic light-emitting diode (oled) |
| CN106518691B (zh) * | 2016-10-28 | 2018-06-26 | 南京工业大学 | 钙钛矿太阳能电池中一类修饰材料-三苯胺衍生物的合成及其应用 |
| EP3401305A1 (en) | 2017-05-12 | 2018-11-14 | Dottikon Es Holding Ag | Indane derivatives and their use in organic electronics |
| TWI774767B (zh) | 2017-05-12 | 2022-08-21 | 瑞士商多蒂孔股份有限公司 | 茚烷衍生物及其在有機電子產品的用途 |
| US10573766B2 (en) * | 2018-02-01 | 2020-02-25 | Panasonic Corporation | Solar cell |
| EP3650438A1 (en) | 2018-11-09 | 2020-05-13 | Dottikon Es Holding Ag | Di-, tri- and tetraphenylindane derivatives and their use in organic electronics |
| CN110649165A (zh) * | 2019-04-04 | 2020-01-03 | 原秀玲 | 一种以四苯基联苯二胺衍生物为空穴传输材料的钙钛矿电池 |
| CN110123279A (zh) * | 2019-05-21 | 2019-08-16 | 深圳大学 | 一种可拉伸的光电传感器及其制备方法 |
| CN111540807B (zh) * | 2020-04-03 | 2021-10-15 | 华南师范大学 | 一种具有高开路电压的全无机钙钛矿太阳能电池及其制备方法 |
| CN113707816B (zh) * | 2021-08-24 | 2023-07-04 | 江苏盛开高新材料有限公司 | 一种钙钛矿太阳能电池的制备方法 |
| WO2023078824A1 (en) | 2021-11-04 | 2023-05-11 | Dottikon Es Holding Ag | Spiro-(indane-fluorene) type compounds and their use in organic electronics |
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