CN106977491B - 螺[芴-9,9-氧杂蒽]类空穴传输材料及其应用 - Google Patents
螺[芴-9,9-氧杂蒽]类空穴传输材料及其应用 Download PDFInfo
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- CN106977491B CN106977491B CN201710060589.8A CN201710060589A CN106977491B CN 106977491 B CN106977491 B CN 106977491B CN 201710060589 A CN201710060589 A CN 201710060589A CN 106977491 B CN106977491 B CN 106977491B
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- fluorene
- spiro
- xanthene
- transport material
- alkyl
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- 239000000463 material Substances 0.000 title claims abstract description 71
- QQNLHOMPVNTETJ-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 QQNLHOMPVNTETJ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000005525 hole transport Effects 0.000 title claims description 42
- -1 arylamine compound Chemical class 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 125000005647 linker group Chemical group 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 15
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 35
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 125000002541 furyl group Chemical class 0.000 claims description 4
- 125000001544 thienyl group Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 12
- 230000009477 glass transition Effects 0.000 abstract description 10
- 125000003003 spiro group Chemical group 0.000 abstract description 8
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 7
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 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 10
- 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
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 5
- CKZFMJJZECAJCW-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene]-2,7-diamine Chemical compound C1=CC=CC=2OC3=CC=CC=C3C3(C1=2)C1=CC(=CC=C1C=1C=CC(=CC=13)N)N CKZFMJJZECAJCW-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 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
- CYGGERDBQBUNDY-UHFFFAOYSA-N 2,7-dibromospiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC(Br)=CC=C2C2=CC=C(Br)C=C21 CYGGERDBQBUNDY-UHFFFAOYSA-N 0.000 description 4
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000004896 high resolution mass spectrometry Methods 0.000 description 4
- 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 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005580 one pot reaction Methods 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 4
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 description 3
- MNBDZJINQUZDFP-UHFFFAOYSA-N 2-bromospiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=C(Br)C=C21 MNBDZJINQUZDFP-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VCOONNWIINSFBA-UHFFFAOYSA-N 4-methoxy-n-(4-methoxyphenyl)aniline Chemical compound C1=CC(OC)=CC=C1NC1=CC=C(OC)C=C1 VCOONNWIINSFBA-UHFFFAOYSA-N 0.000 description 2
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- LOYYIKDGYOYCSH-UHFFFAOYSA-N [Co].N1(N=CC=C1)C1=NC=CC=C1.N1(N=CC=C1)C1=NC=CC=C1.N1(N=CC=C1)C1=NC=CC=C1 Chemical compound [Co].N1(N=CC=C1)C1=NC=CC=C1.N1(N=CC=C1)C1=NC=CC=C1.N1(N=CC=C1)C1=NC=CC=C1 LOYYIKDGYOYCSH-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 235000008434 ginseng Nutrition 0.000 description 2
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 125000005259 triarylamine group Chemical group 0.000 description 2
- UPJLZKCEPFAKSH-UHFFFAOYSA-N 2',7'-dibromo-9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC(Br)=CC=C1C1=CC=C(Br)C=C12 UPJLZKCEPFAKSH-UHFFFAOYSA-N 0.000 description 1
- QQTBEFPDRHYPLE-UHFFFAOYSA-N 2,7-dibromo-9,9-dipropylfluorene Chemical compound C1=C(Br)C=C2C(CCC)(CCC)C3=CC(Br)=CC=C3C2=C1 QQTBEFPDRHYPLE-UHFFFAOYSA-N 0.000 description 1
- JUZPYVOOFVEYJW-UHFFFAOYSA-N 2,7-dibromo-9-(4-methoxyphenyl)carbazole Chemical compound BrC1=CC=2N(C3=CC(=CC=C3C=2C=C1)Br)C1=CC=C(C=C1)OC JUZPYVOOFVEYJW-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 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 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001894 space-charge-limited current method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- 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
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- 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
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Abstract
一种螺[芴‑9,9‑氧杂蒽]类空穴传输材料及其应用,所述材料是以螺[芴‑9,9‑氧杂蒽]为核壳结构的芳胺类化合物,该所述合物中含有1个以上的N‑核结构单元,相邻的两个N‑核结构单元通过连接基团相连,所述的N‑核结构单元符合通式F:Rx、Ry和Rz是取代基或连接基团。本发明所述的材料为多螺[芴‑9,9‑氧杂蒽]为核壳结构的芳胺类化合物。相对于现有同类产品,具有更高的玻璃转化温度和热分解温度;具有更高的氧化还原电位;具有更高的空穴迁移率和导电率;在钙钛矿太阳能电池和其他的有机电子器件领域有巨大的应用价值和广阔的应用前景。
Description
技术领域
本发明涉及一类螺[芴-9,9-氧杂蒽]类空穴传输材料及其制备方法,并涉及这类材料在钙钛矿太阳能电池,有机太阳能电池,有机电致发光器件,有机场效应晶体管,有机光探测器,有机激光,有机非线性光学,有机电存储和化学与生物传感等领域的应用。属于有机半导体和光电材料技术领域。
技术背景
自2009年,日本桐荫横滨大学教授Tsutomu Miyasaka首次报道了一种基于钙钛矿型晶体结构(CH3NH3PbX3,X代表卤族元素)为吸光材料的太阳能电池以来(J.Am.Chem.Soc.,2009,131(17),pp 6050–6051),钙钛矿太阳能电池(perovskite solar cells)引起了全世界的广泛关注。在过去短短的7年时间里,钙钛矿太阳电池的的效率已经从当初的3.8%提高到了22.1%(Nature Energy,2016,doi:10.1038/nenergy.2016.142)。其效率已经完全可以跟晶体硅太阳能电池的光电转化效率相媲美。更重要的是,钙钛矿晶体材料有很高的摩尔消光系数,高达105。通过调节钙钛矿材料的组成,可改变其带隙和吸收光谱,制备各种颜色的电池器件。另外,钙钛矿太阳电池还具有成本低,制备工艺简单,以及可制备柔性、透明及叠层电池等一系列优点,从而显示出了广泛的应用前景。
空穴传输材料一般用在钙钛矿层和金属电极之间,以改善肖特基(Schottky)接触,促使电子和空穴在功能层界面分离,减少电荷复合,同时有利于空穴传输,提高电池性能。目前在钙钛矿太阳能电池中使用最广泛的是有机小分子空穴传输材料2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴(spiro-OMeTAD),其光电转换效率达21.6%。但该分子的核壳结构9,9-螺二芴的合成需要用到无水无氧反应,而且步骤繁多,总收率较低,大规模制备受到一定的限制。更重要的是,spiro-OMeTAD的空穴迁移率和导电率较低,热稳定性较差和氧化还原电位较低,使用受到一定限制。单螺[芴-9,9-氧杂蒽]为核的空穴传输材料,如X59,虽然合成较为简单,但是由于其玻璃转化温度(Tg)和热分解温度(Td)不高,空穴迁移率和导电率也一般,在钙钛矿电池中的应用也受到一定的限制。
此外,还有聚三芳胺空穴传输材料(PTAA),其光电转化效率也高达20%以上,但其合成步骤比较多,纯化比较困难,生产成本比较高,极大的限制了钙钛矿太阳能电池今后的大规模应用。因此,开发低成本,高效率,高稳定性的和具有市场潜力的有机空穴传输材料应用于钙钛矿太阳能电池引起了全世界科学家和各大企业的广泛关注和投入。
综上可见尽管现有的螺[芴-9,9-氧杂蒽]类空穴传输材料由于具有垂直的螺环结构而能够有效的抑制分子间的π-π堆积作用,从而在溶解性,热稳定性等各方面具有优异的表现,但仍然存在各种缺陷导致其在实际的商业应用中受到限制。
发明内容
本发明的目的之一,便在于基于现有的螺[芴-9,9-氧杂蒽]类空穴传输材料,对该类结构的化合物进行结构的优化设计与改进,以期获得具有更加优良的市场应用价值的材料物质。
基于此,本发明首先提供一类螺[芴-9,9-氧杂蒽]类空穴传输材料,是以螺[芴-9,9-氧杂蒽]为核壳结构的芳胺类化合物,该所述化合物中含有1个以上的N-核结构单元,相邻的两个N-核结构单元通过连接基团相连,所述的N-核结构单元符合通式F:
Rx、Ry和Rz是取代基或连接基团;
其中,取代基各自独立地是R、苯基或取代苯基;
所述的取代苯基是由下述基团任意取代的苯基:卤素,-OH,C1-6烷基或C1-6烷氧基;
所述的连接基团选自式i~xv的基团:
式R所示的取代基和式i~xv所示的连接基团中,R1~21各自独立地选自-H,卤素,-OH,C1-6烷基,C1-6烷基取代苯基,C1-6烷氧基取代苯基,C1-6烷基取代噻吩基或者C1-6烷基取代呋喃基。
上述本发明的螺[芴-9,9-氧杂蒽]类空穴传输材料事实上是一类含有多螺[芴-9,9-氧杂蒽结构的芳胺类化合物。相对于现有技术中单螺[芴-9,9-氧杂蒽]为核壳结构的芳胺类有机空穴传输材料而言,本发明的化合物具有以下突出优势:
①更高的玻璃转化温度(Tg)和热分解温度(Td),显示出更好的热稳定性;
②更高的氧化还原电位,有利于在钙钛矿太阳能电池器件中获得更高的开路电压;
③更高的空穴迁移率和导电率,有利于在在钙钛矿太阳能电池器件中更高效的分离和传输电荷;
④在氯苯、邻二氯苯和甲苯中有好的溶解性,有利于溶液法制备有机薄膜;
⑤合成和纯化方法简单,有利于大规模商业化制备;
⑥在钙钛矿太阳能电池中有很好的器件性能,其器件的光电转化效率高达20%以上,已经基本具备了商业化应用的潜力。
表明该系列化合物作为有机空穴传输材料将在钙钛矿太阳能电池和其他的有机电子器件领域有巨大的应用价值和广阔的应用前景,具体的应用领域可举例但不限于有机太阳能电池,有机电致发光器件,有机场效应晶体管,有机光探测器,有机激光,有机非线性光学,有机电存储和化学与生物传感等。
因此,本发明另一方面还提供所述螺[芴-9,9-氧杂蒽]类空穴传输材料在制备钙钛矿太阳能电池中的应用。
附图说明
本发明附图3幅,其中:
图1是钙钛矿太阳能电池标准器件结构示意图。
图2是参测材料的电化学循环伏安图。
图3是参测的材料的钙钛矿太阳能电池器件的电压和电流密度曲线图。
具体实施方式
螺[芴-9,9-氧杂蒽]类空穴传输材料由于具有垂直的螺环结构而能够有效的抑制分子间的π-π堆积作用,从而具有优良的溶解性及热稳定性。本发明提供一种新的螺[芴-9,9-氧杂蒽]类空穴传输材料,是以螺[芴-9,9-氧杂蒽]为核壳结构的芳胺类化合物,所述化合物中含有1个以上的N-核结构单元,相邻的两个N-核结构单元通过连接基团相连,所述的N-核结构单元符合通式F:
本发明所提供的螺[芴-9,9-氧杂蒽]类空穴传输材料其本质是一类具有多螺[芴-9,9-氧杂蒽]类核壳结构的芳胺类化合物,具有通式F的基础结构单元,即N-核结构单元,在化合物中重复出现。相邻两个N-核结构单元通过连接基团相连,从而实现分子式的延伸。
本发明所述的螺[芴-9,9-氧杂蒽]类空穴传输材料中,所述的通式F中的Rx、Ry和Rz中至少一个是连接基团,以保证化合物中的N-核结构单元是相连的2个或2个以上。一般情况下,本发明中相邻两个N-核结构单元共用同一个连接基团。这种重复的N-核结构单元,在本发明中出现的目的在于提供多个螺[芴-9,9-氧杂蒽]以及多个N-核的芳胺中心。F通式的N-核结构单元出现的次数,即所述的化合物中含有的N-核结构单元是2~10个,优选2~6个。化合物中N-核结构单元的个数以及Rx、Ry和Rz的选择共同决定化合物中螺[芴-9,9-氧杂蒽]结构单位的个数。或更具体地,螺[芴-9,9-氧杂蒽]结构单位的个数可以表达为化合物中结构为R或式x的基团的总数。为实现本发明的目的,要求螺[芴-9,9-氧杂蒽]结构单位的个数为2个或2个以上。优选化合物中螺[芴-9,9-氧杂蒽]结构单位总数3~7个。
如上文所述,本发明通式F中,Rx、Ry和Rz中有1个或2个是取代基;所述的取代基各自独立地是R、苯基或取代苯基;
所述的式R的取代基中,上述连接基团中,R1和R2各自独立地选自-H,卤素,-OH,C1-6烷基,C1-6烷基取代苯基,C1-6烷氧基取代苯基,C1-6烷基取代噻吩基或者C1-6烷基取代呋喃基;优选地,所述的R1和R2各自独立地选自-H,卤素,-OH,C1-6烷基,C1-6烷基取代苯基,C1-6烷氧基取代苯基。更优选的实施方式中,所述的R1和R2各自独立地选自-H、C1-6烷基,C1-6烷基取代苯基和C1-6烷氧基取代苯基。上述结构中,涉及螺[芴-9,9-氧杂蒽]结构的,又尤为优选氧杂蒽结构单元优选对称对待,所述的对称取代包括但不限于均为H取代,即未取代的结构。
最为优选的,所述的R1和R2均为H。
上文中所述的取代苯基是由下述基团任意取代的苯基:卤素,-OH,C1-6烷基或C1-6烷氧基;在本说明书中所提及的任意取代,如无特殊说明,均应当按照本领域的常规理解来解释,上述任意取代的苯基则是指任意数量的取代基在苯基任意位置的取代。
作为优选的方式,所述的取代基各自独立地是R、苯基、C1-6烷基任意取代的苯基、C1-6烷氧基任意取代的苯基;更优选地,所述的取代基各自独立地是R、苯基、C1-6烷氧基单取代的苯基;进一步优选R、苯基、C1-6烷氧基对位取代苯基;最优选R、苯基、C1-4烷氧基对位取代苯基;尤其优选R、苯基、对甲氧基苯基,其中,R1和R2是H。
本发明通式F中,Rx、Ry和Rz中至少有1个连接基团,所述的连接基团选自式i~xv的基团:
上述连接基团中,R3~21各自独立地选自-H,卤素,-OH,C1-6烷基,C1-6烷基取代苯基,C1-6烷氧基取代苯基,C1-6烷基取代噻吩基或者C1-6烷基取代呋喃基;优选地,所述的R3~21各自独立地选自-H,卤素,-OH,C1-6烷基,C1-6烷基取代苯基,C1-6烷氧基取代苯基。更优选的实施方式中,所述的R3~21各自独立地选自-H、C1-6烷基,C1-6烷基取代苯基和C1-6烷氧基取代苯基。
更为具体的实施方式中,本发明中所述及的连接基团选自下述基团:
其中又以式i、ii或x的连接基团最为优选。
上述关于连接基团的结构描述中,涉及螺[芴-9,9-氧杂蒽]结构的,又尤为优选氧杂蒽结构单元优选对称对待,所述的对称取代包括但不限于均为H取代,即未取代的结构。
更加具体地,上述本发明的螺[芴-9,9-氧杂蒽]类空穴传输材料,是选自如下结构的化合物:
尤其优选式X26、X36、X37、X54、X55和X56的化合物,分别是:
X26:N2-(2-(双(4-甲氧基苯)胺)螺[芴-9,9'-氧杂蒽]-7-基)-N2,N7,N7-四(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2,7-二胺;
X36:N2,N2”-([1,1'-联苯]-4,4'-二基)双(N2,N7,N7-四(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2,7-二胺;
X37:N2,N2”-(螺[芴-9,9'-氧杂蒽]-2,7-二基)双(N2,N7,N7-四(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2,7-二胺;
X54:N4,N4'-二(4-甲氧基苯)螺-N4,N4'-二螺[芴-9,9'-氧杂蒽]-2-基)-[1,1'-二联苯]-4,4'-二胺;
X55:N2,N7-二(4-甲氧基苯)-N2,N7-二螺[芴-9,9'-氧杂蒽]-2-基)螺[芴-9,9'-氧杂蒽]-2,7-二胺;
X56:N2,N2,N7,N7-四(螺[芴-9,9'-氧杂蒽]-2-基)螺[芴-9,9'-氧杂蒽]-2,7-二胺。
本发明的螺[芴-9,9-氧杂蒽]类空穴传输材料的制备方法根据所需要制备的不同N-核结构单元个数而采取不同的合成方案。根据目标产物中N-核结构单元个数和螺[芴-9,9-氧杂蒽]数目,本领域的技术人员可以根据现有技术指定适当的合成方案。本申请人首先提供一类较为具体的产物的合成方法,旨在引导本领域技术人员使用类似的方法来完成其它化合物的合成。所述的合成方法包括如下步骤:
(1)在氮气保护下,室温下,两口烧瓶中加入干燥的甲苯,3摩尔份的2,7-二溴螺[芴-9,9-氧杂蒽],0.02摩尔份的醋酸钯,0.04摩尔份的1,1'-双(二苯基膦)二茂铁,4,4'-二甲氧基二苯胺1摩尔份的和1.5摩尔份的叔丁醇钠(0.29g,3.0mmol)在100摄氏度下反应搅拌过夜。冷却后,用水淬灭反应,乙酸乙酯萃取,无水硫酸钠干燥,硅胶柱层析分离,得到淡黄色固体,经鉴定为7-溴-N,N-双(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2-胺,TBrSFX。
(2)2.2摩尔份的TBrSFX,1摩尔份的对甲氧基苯胺,2.5摩尔份的叔丁醇钠,0.01摩尔份的醋酸钯,0.01摩尔份的三叔丁基膦和干燥的甲苯,加入到史莱克瓶中,反应体系用双排管置换三次去水除氧,然后升温至100摄氏度,反应过夜。冷却后,用水淬灭反应,乙酸乙酯萃取,无水硫酸钠干燥,硅胶柱层析分离,得到淡黄色固体粉末,X26。
(3)利用一锅法布赫瓦尔德(Buchwald)反应制备最终产物:在氮气保护下,室温下,两口烧瓶中加入干燥的甲苯,0.06摩尔份的三(二亚苄基丙酮)二钯,0.1摩尔份的1,1'-双(二苯基膦)二茂铁(DPPF)和1摩尔份的2,7-二溴螺[芴-9,9-氧杂蒽],(或者4,4'-二溴-1,1'-联苯,或者2,7-二溴-9-(4-甲氧基苯基)-9H-咔唑,或者2,7-二溴-9,9-二丙基-9H-芴,或者2,7-二溴-9,9'-螺二芴,或者2,7-二溴螺[芴-9,9'-硫杂蒽]10',10'-二氧)搅拌10分钟。接着,2.5摩尔份的叔丁醇钠和2摩尔份的对甲氧基苯胺加入到此溶液中,升温到90摄氏度,反应8小时。此后,用TLC点板跟踪,直到原料点消失。然后,再加入2.5摩尔份的叔丁醇钠,2.1摩尔份的2-溴螺[芴-9,9-氧杂蒽](或者7-溴-N,N-双(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2-胺(TBrSFX))和甲苯。此溶液升温至100摄氏度,搅拌过夜。反应完后,冷却,用水淬灭反应,用乙酸乙酯萃取,硫酸钠干燥,硅胶柱层析分离,分别得到淡黄色固体粉末X36,X37,X54,X55,X56,X57,X58,X67,X68,X55。
上述方法描述了X26、X36,X37,X54,X55,X56,X57,X58,X67,X68及X55的制备方法。由该方法经过简单的变换,选用相应的原料物,比如在步骤(1)中使用相应的R2和R3取代的二溴螺[芴-9,9-氧杂蒽]为原料,即可获得产物中相应位置有R2和R3取代的产物。而根据现有技术,本领域的技术人员完全可以独立实现R2和R3取代的二溴螺[芴-9,9-氧杂蒽]的合成,并完成本发明。
另一方面,上述方法详细描述的极优选化合物X26,X36,X37,X54,X55,X56,X57,X58,X67,X68和X55中含有2~4个N-核结构单元。而含有4~10个N-核结构单元的化合物,经过重复使用简单的化学反应方法,比如用布赫瓦尔德(Buchwald)和铃木反应(Suzuki)等,和选用相应的原料反应物即可获得。申请人相信,本领域的技术人员根据目标产物的结构,结合上述合成方法的描述,完全可以设计实施相应的方法完成合成,实现本发明的目的。
下述非限制性实施例用于进一步说明本发明的内容,不应当被理解为对本发明任意形式的限定。
实施例1
N2-(2-(双(4-甲氧基苯)胺)螺[芴-9,9'-氧杂蒽]-7-基)-N2,N7,N7-四(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2,7-二胺(X26)的合成,按照如下路线:
(1)7-溴-N,N-双(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2-胺(TBrSFX)的合成:
在氮气保护下,室温下,两口烧瓶中加入干燥的甲苯(20ml),2,7-二溴螺[芴-9,9-氧杂蒽](2.94g,6.0mmol),醋酸钯(9.0mg,0.04mmol),1,1'-双(二苯基膦)二茂铁(44.4mg,0.08mmol),4,4'-二甲氧基二苯胺(0.46g,2.0mmol)和叔丁醇钠(0.29g,3.0mmol)在100摄氏度下反应搅拌过夜。冷却后,用水淬灭反应,乙酸乙酯萃取,无水硫酸钠干燥,硅胶柱层析分离,得到淡黄色固体1.00g,收率为78%。经鉴定为7-溴-N,N-双(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2-胺。
1H NMR(400MHz,d6-DMSO,298K),δ(ppm):7.78(d,J=8Hz,1H),7.75(d,J=8Hz,1H),7.51(d,J=8Hz,1H),7.27~7.24(m,4H),7.08(s,1H),6.91(d,J=8Hz,6H),6.80(d,J=4Hz,5H),6.49(s,1H),6.42(d,J=8Hz,2H),3.68(s,6H,OMe)。
(2)N2-(2-(双(4-甲氧基苯)胺)螺[芴-9,9'-氧杂蒽]-7-基)-N2,N7,N7-四(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2,7-二胺(X26)的合成:
TBrSFX(639mg,1.00mmol),对甲氧基苯胺(56mg,0.46mmol),叔丁醇钠(109mg,1.14mmol),醋酸钯(4mg,0.02mmol),三叔丁基膦(4mg,0.02mmol)和10mL甲苯,加入到50mL史莱克瓶中,反应体系用双排管置换三次去水除氧,然后升温至100摄氏度,反应过夜。冷却后,用水淬灭反应,乙酸乙酯萃取,无水硫酸钠干燥,硅胶柱层析分离,得到淡黄色固体,461mg,收率81%。经鉴定为N2-(2-(双(4-甲氧基苯)胺)螺[芴-9,9'-氧杂蒽]-7-基)-N2,N7,N7-四(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2,7-二胺(X26)。
1H NMR(400MHz,d6-DMSO,298K),δ(ppm):7.58(d,J=8Hz,2H),7.53(d,J=8Hz,2H),7.22(t,J=8Hz,4H),7.11(d,J=8Hz,4H),6.91~6.67(m,26H),6.62(d,J=8Hz,2H),6.53(s,2H),6.48(s,2H),6.42(d,J=8Hz,4H),3.68(s,12H,OMe),3.63(s,3H,OMe).13CNMR(400MHz,C6D6,298K),δ(ppm):156.91,156.50,156.28,156.14,151.88,149.01,147.83,141.37,140.61,134.75,132.68,126.95,126.53,125.92,123.56,121.27,120.75,120.01,118.56,117.15,114.94,114.78,54.98,54.88,54.68.HR-MS(ESI)m/z:[M+1]+calcd for 1237.4666;found,1238.4619.
实施例2
N2,N2”-([1,1'-联苯]-4,4'-二基)双(N2,N7,N7-四(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2,7-二胺(X36)的合成,按照如下路线:
具体是利用一锅法布赫瓦尔德(Buchwald)反应制备最终产物:在氮气保护下,室温下,两口烧瓶中加入干燥的甲苯(10mL),三(二亚苄基丙酮)二钯(3.1mg,0.03mmol),1,1'-双(二苯基膦)二茂铁(DPPF)(5.2mg,0.05mmol)和4,4'-二溴-1,1'-联苯(156mg,0.5mmol),搅拌10分钟。接着,叔丁醇钠(120mg,1.25mmol)和对甲氧基苯胺(123mg,1.00mmol)加入到此溶液中,升温到90摄氏度,反应8小时。此后,用TLC点板跟踪,直到原料点消失。然后,再加入叔丁醇钠(120mg,1.25mmol),TBrSFX(670.5mg,1.05mmol)和甲苯。此溶液升温至100摄氏度,搅拌过夜。反应完后,冷却,用水淬灭反应,用乙酸乙酯萃取,硫酸钠干燥,硅胶柱层析分离,得到淡黄色固体590mg,收率78%。经鉴定为N2,N2”-([1,1'-联苯]-4,4'-二基)双(N2,N7,N7-四(4-甲氧基苯)螺[芴-9,9'-氧杂蒽]-2,7-二胺
1H NMR(400MHz,d6-DMSO,298K),δ(ppm):7.66(d,J=8Hz,2H),7.62(d,J=8Hz,2H),7.31~7.23(m,8H),7.13(d,J=8Hz,4H),6.93~6.71(m,36H),6.65(s,2H),6.50(d,J=8Hz,6H),3.68(s,6H,OMe),3.70(s,12H,OMe).13C NMR(400MHz,C6D6,298K),δ(ppm):156.75,156.68,156.47,156.34,151.95,149.13,147.98,147.27,141.36,140.85,134.73,134.58,132.95,127.51,127.44,126.60,126.00,123.58,123.37,123.26,121.31,120.80,120.28,120.16,118.60,117.26,115.07,114.97,55.05,54.89.HR-MS(ESI)m/z:[M+1]+calcd for 1510.5820;found,1511.5848.
实施例3
N4,N4'-二(4-甲氧基苯)螺-N4,N4'-二螺[芴-9,9'-氧杂蒽]-2-基)-[1,1'-二联苯]-4,4'-二胺(X54)的合成,按照如下线路:
利用一锅法布赫瓦尔德(Buchwald)反应制备最终产物:在氮气保护下,室温下,两口烧瓶中加入干燥的甲苯(10mL),三(二亚苄基丙酮)二钯(6.2mg,0.06mmol),1,1'-双(二苯基膦)二茂铁(DPPF)(10.3mg,0.1mmol)和4,4'-二溴-1,1'-联苯(312mg,1.00mmol),搅拌10分钟。接着,叔丁醇钠(240mg,2.50mmol)和对甲氧基苯胺(246mg,2.00mmol)加入到此溶液中,升温到90摄氏度,反应8小时。此后,用TLC点板跟踪,直到原料点消失。然后,再加入叔丁醇钠(120mg,1.25mmol),2-溴螺[芴-9,9-氧杂蒽](863.7mg,2.10mmol)和甲苯。此溶液升温至100摄氏度,搅拌过夜。反应完后,冷却,用水淬灭反应,用乙酸乙酯萃取,硫酸钠干燥,硅胶柱层析分离,得到淡黄色固体856mg,收率81%。经鉴定为N4,N4'-二(4-甲氧基苯)螺-N4,N4'-二螺[芴-9,9'-氧杂蒽]-2-基)-[1,1'-二联苯]-4,4'-二胺(X54)。
1H NMR(400MHz,d6-DMSO,298K),δ(ppm):7.85(t,J=8Hz,4H),7.35(d,J=8Hz,6H),7.28~7.21(m,8H),7.14(t,J=8Hz,2H),7.03~6.83(m,20H),6.68(s,2H),6.42(d,J=8Hz,4H),3.71(s,6H,OMe).13C NMR(400MHz,C6D6,298K),δ(ppm):156.99,156.91,155.61,151.95,149.10,147.16,140.68,139.91,134.96,134.27,127.58,126.08,125.65,123.67,123.54,122.95,121.02,120.36,119.48,117.19,115.12,54.93,54.89.HR-MS(ESI)m/z:[M+1]+calcd for 1056.3927;found,1056.3943.
实施例四
N2,N7-二(4-甲氧基苯)-N2,N7-二螺[芴-9,9'-氧杂蒽]-2-基)螺[芴-9,9'-氧杂蒽]-2,7-二胺(X55)的合成,按照下述合成路线:
利用一锅法布赫瓦尔德(Buchwald)反应制备最终产物:在氮气保护下,室温下,两口烧瓶中加入干燥的甲苯(10mL),三(二亚苄基丙酮)二钯(6.2mg,0.06mmol),1,1'-双(二苯基膦)二茂铁(DPPF)(10.3mg,0.1mmol)和2,7-二溴螺[芴-9,9-氧杂蒽](4.90mg,1.0mmol),搅拌10分钟。接着,叔丁醇钠(240mg,2.50mmol)和对甲氧基苯胺(246mg,2.00mmol)加入到此溶液中,升温到90摄氏度,反应8小时。此后,用TLC点板跟踪,直到原料点消失。然后,再加入叔丁醇钠(120mg,1.25mmol),2-溴螺[芴-9,9-氧杂蒽](863.7mg,2.10mmol)和甲苯。此溶液升温至100摄氏度,搅拌过夜。反应完后,冷却,用水淬灭反应,用乙酸乙酯萃取,硫酸钠干燥,硅胶柱层析分离,得到淡黄色固体1037mg,收率84%。经鉴定为N2,N7-二(4-甲氧基苯)-N2,N7-二螺[芴-9,9'-氧杂蒽]-2-基)螺[芴-9,9'-氧杂蒽]-2,7-二胺(X55)。
1H NMR(400MHz,d6-DMSO,298K),δ(ppm):7.80(d,J=8Hz,2H),7.73(d,J=8Hz,2H),7.59(d,J=8Hz,2H),7.33~7.19(m,12H),7.11(t,J=8Hz,4H),6.97(d,J=8Hz,2H),6.88~6.85(m,10H),6.77(d,J=8Hz,4H),6.65(d,J=8Hz,4H),6.56(d,J=8Hz,4H),6.39(d,J=8Hz,2H),6.34(d,J=8Hz,4H),3.63(s,6H,OMe).13C NMR(400MHz,C6D6,298K),δ(ppm):156.69,155.82,151.87,151.77,148.85,147.86,140.35,139.61,134.45,134.29,128.18,127.95,127.15,125.94,125.57,123.66,123.59,122.94,122.53,120.84,120.78,120.34,120.23,119.44,117.16,117.11,114.81,54.90,54.85,54.68.HR-MS(ESI)m/z:[M+1]+calcd for1234.4346;found,1234.4359.
实施例5
空穴传输材料氧化还原电位的测试试验
参测的材料分别是X59、X26、X36、X55和Spiro-OMeTAD。其中,X59和Spiro-OMeTAD是单核材料,X26和X36是双核材料,X55是三核材料。
电化学循环伏安(CV)在电化学工作站(model 660A)上测试进行,采用三电极,Ag/0.01M AgNO3为参比电极,玻璃碳为工作电极,铂丝为对电极,二氯甲烷为溶剂,六氟磷四丁基胺(n-Bu4NPF6)作为电解质,浓度为0.1M,扫速为50mV/s,使用二茂铁为基准。CV图见附件图2,其氧化还原电位换算成标准氢电极以后的数据见表1。
由图2中,我们可以换算出参测材料的氧化还原电位数值分别为:X59为0.61V,X26为0.66V,X36为0.68V,X55为0.73V,spiro-OMeTAD为0.62V(见表1)。由此可见多核螺[芴-9,9-氧杂蒽]类空穴传输材料的氧化还原电位普遍要比单核的高一些。
表1
实施例6
空穴传输材料的空穴迁移率和导电率的测试试验
参测的材料与实施例5相同。
利用空间电荷限制电流法和两点探针法分别测试此类空穴传输材料的空穴迁移率和导电率。空穴迁移率的器件结构为:ITO/PEDOT:PSS/螺[芴-9,9-氧杂蒽]类空穴传输材料层/三氧化钼/金属电极。导电率的器件结构为:玻璃基底/多孔的二氧化钛层/螺[芴-9,9-氧杂蒽]类空穴传输材料层/金属电极。其中空穴传输材料层采用旋涂法,浓度为70mg/mL在干燥的氯苯中,同时,掺杂4-叔丁基吡啶(4-tert-butylpyridine,TBP),双三氟甲烷磺酰亚胺锂盐(lithium bis(trifluoromethanesulfonyl)imide,Li-TFSI)和p型掺杂剂三(2-(1H吡唑-1-基)吡啶)合钴(tris(2-(1Hpyrazol-1-yl)pyridine)cobalt(III),FK102)。
通过拟合计算出来的空穴迁移率和导电率数据见表1。由表中数据,我们可以看出多核螺[芴-9,9-氧杂蒽]类空穴传输材料(X26,X36和X55)的空穴迁移率和导电率普遍要比单核(X59和spiro-OMeTAD)的高一些。
实施例7
使用不同的空穴传输材料制作钙钛矿太阳能电池的器件,并检测其光电转化效率。参测的材料包括Spiro-OMeTAD(单核)、X26(双核)、X36(双核)和X55(三核)。
其器件结构为:FTO/致密的二氧化钛层/多孔的二氧化钛层/钙钛矿吸光层/螺[芴-9,9-氧杂蒽]类空穴传输材料层/金属电极。其中空穴传输材料层采用旋涂法,浓度为70mg/mL在干燥的氯苯中,同时,掺杂4-叔丁基吡啶(4-tert-butylpyridine,TBP),双三氟甲烷磺酰亚胺锂盐(lithium bis(trifluoromethanesulfonyl)imide,Li-TFSI)和p型掺杂剂三(2-(1H吡唑-1-基)吡啶)合钴(tris(2-(1Hpyrazol-1-yl)pyridine)cobalt(III),FK102)。器件的光电转化效率图见附件图3,具体参数见表2。
表2
参测材料 | 光电转化效率 | 开路电压 | 短路电流 | 填充因子 |
Spiro-OMeTAD | 18.8 | 1.13 | 23.1 | 72.0 |
X26 | 20.2 | 1.11 | 24.3 | 74.5 |
X36 | 18.9 | 1.06 | 23.7 | 76.0 |
X55 | 20.8 | 1.15 | 23.4 | 77.4 |
从表2的结果可以看出多核螺[芴-9,9-氧杂蒽]类空穴传输材料(X26,X36和X55)的光电转化效率和短路电流密度都要比单核的spiro-OMeTAD都要高。
实施例8
空穴传输材料的玻璃转化温度(Tg)和分解温度测试(Td)
参测的材料分别是X26、X36、X55、X39、X56、X57、X58和Spiro-OMeTAD。其中,Spiro-OMeTAD是单核材料,X26和X36、X39、X58是双核材料,X55和X57是三核材料,X56是五核材料。
本实验采用差示扫描量热法(DSC)来测试这一系列材料的玻璃转化温度(Tg),使用的仪器型号为Mettler Toledo,在氮气氛围下扫速为10℃/min,同过获得的差示扫描量热法曲线可以获得材料的玻璃转化温度。热重分析(TGA)测试仪为Mettler Toledo,在氮气氛围下扫速为10℃/min,同过获得的热重分析曲线的起始点可以获得材料的玻璃转化温度。材料的具体的玻璃转化温度和热分解温度见表3。
由表3中测得的数据可看出,多核螺[芴-9,9-氧杂蒽]类空穴传输材料的玻璃转化温度和热分解温度普遍要比单核的高一些。
表3
参测材料 | X26 | X36 | X39 | X55 | X56 | X57 | X58 | Spiro |
玻璃转化温度 | 155.2 | 164.6 | 181.5 | 175.4 | 192.8 | 179.3 | 160.1 | 121.1 |
热分解温度 | 438.2 | 439.0 | 441.5 | 446.4 | 457.8 | 446.1 | 437.6 | 421.9 |
Claims (7)
1.螺[芴-9,9-氧杂蒽]类空穴传输材料,是以螺[芴-9,9-氧杂蒽]为核壳结构的芳胺类化合物,其特征在于,所述化合物中含有2~4个N-核结构单元,相邻的两个N-核结构单元通过连接基团相连,所述的N-核结构单元符合通式F:
Rx、Ry和Rz是取代基或连接基团,所述的Rx、Ry和Rz中至少一个是连接基团;
其中,取代基各自独立地是R、苯基或取代苯基;
所述的取代苯基是由下述基团任意取代的苯基:卤素,-OH,C1-6烷基或C1-6烷氧基;
所述的连接基团选自式i~xv的基团:
式R所示的取代基和式i~xv所示的连接基团中,R1~21各自独立地选自-H,卤素,-OH,C1-6烷基,C1-6烷基取代苯基,C1-6烷氧基取代苯基,C1-6烷基取代噻吩基或者C1-6烷基取代呋喃基;
所述的化合物中结构为R或式x的基团总数为2~5个。
2.根据权利要求1所述的螺[芴-9,9-氧杂蒽]类空穴传输材料,其特征在于,所述的式R的取代基团和式i~xv的连接基团中,所述的R1~21各自独立地选自-H,卤素,-OH,C1-6烷基,C1-6烷基取代苯基,C1-6烷氧基取代苯基。
3.根据权利要求2所述的螺[芴-9,9-氧杂蒽]类空穴传输材料,其特征在于,所述的R1~21各自独立地选自-H、C1-6烷基,C1-6烷基取代苯基和C1-6烷氧基取代苯基。
5.根据权利要求3所述的螺[芴-9,9-氧杂蒽]类空穴传输材料,其特征在于,所述的取代基各自独立地是R、苯基、C1-6烷基任意取代的苯基、C1-6烷氧基任意取代的苯基。
7.权利要求1所述的螺[芴-9,9-氧杂蒽]类空穴传输材料在制备钙钛矿太阳能电池中的应用。
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KR20210007782A (ko) * | 2019-07-10 | 2021-01-20 | 덕산네오룩스 주식회사 | 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치 |
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