WO2016150215A1 - 离子型阴极缓冲层分子型材料及其制备方法和应用 - Google Patents
离子型阴极缓冲层分子型材料及其制备方法和应用 Download PDFInfo
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- WO2016150215A1 WO2016150215A1 PCT/CN2015/098525 CN2015098525W WO2016150215A1 WO 2016150215 A1 WO2016150215 A1 WO 2016150215A1 CN 2015098525 W CN2015098525 W CN 2015098525W WO 2016150215 A1 WO2016150215 A1 WO 2016150215A1
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- buffer layer
- target product
- cathode buffer
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 239000000872 buffer Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 125000001246 bromo group Chemical group Br* 0.000 claims description 15
- -1 alkyl ion Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 8
- 238000013086 organic photovoltaic Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 230000005669 field effect Effects 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000005401 electroluminescence Methods 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 12
- 230000003628 erosive effect Effects 0.000 abstract description 6
- 150000003384 small molecules Chemical class 0.000 abstract description 5
- 238000010129 solution processing Methods 0.000 abstract description 4
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000010410 layer Substances 0.000 description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 21
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- DZAUEKJDFUYCNK-UHFFFAOYSA-N (6-bromonaphthalen-2-yl)-diphenylphosphane Chemical compound C1=CC2=CC(Br)=CC=C2C=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 DZAUEKJDFUYCNK-UHFFFAOYSA-N 0.000 description 5
- LTMXAEJTVUINSL-UHFFFAOYSA-N 2-bromo-6-diphenylphosphorylnaphthalene Chemical compound C1=CC2=CC(Br)=CC=C2C=C1P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 LTMXAEJTVUINSL-UHFFFAOYSA-N 0.000 description 5
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WTWVYZKNBKFYHA-UHFFFAOYSA-N BrC1=CC2=CC=C(C=C2C=C1)OCCCN(C)C Chemical compound BrC1=CC2=CC=C(C=C2C=C1)OCCCN(C)C WTWVYZKNBKFYHA-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 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 2
- PJZDEYKZSZWFPX-UHFFFAOYSA-N 2,6-dibromonaphthalene Chemical compound C1=C(Br)C=CC2=CC(Br)=CC=C21 PJZDEYKZSZWFPX-UHFFFAOYSA-N 0.000 description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 2
- OADZHFGJIVKDJN-UHFFFAOYSA-N 3-bromo-1,10-phenanthroline Chemical compound C1=CN=C2C3=NC=C(Br)C=C3C=CC2=C1 OADZHFGJIVKDJN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- LJQNMDZRCXJETK-UHFFFAOYSA-N 3-chloro-n,n-dimethylpropan-1-amine;hydron;chloride Chemical compound Cl.CN(C)CCCCl LJQNMDZRCXJETK-UHFFFAOYSA-N 0.000 description 1
- YLDFTMJPQJXGSS-UHFFFAOYSA-N 6-bromo-2-naphthol Chemical compound C1=C(Br)C=CC2=CC(O)=CC=C21 YLDFTMJPQJXGSS-UHFFFAOYSA-N 0.000 description 1
- MMJLKBCDTFTSCT-UHFFFAOYSA-N CC1(C)OB(c(cc2)cc(cc3)c2cc3P(c2ccccc2)(c2ccccc2)=O)OC1(C)C Chemical compound CC1(C)OB(c(cc2)cc(cc3)c2cc3P(c2ccccc2)(c2ccccc2)=O)OC1(C)C MMJLKBCDTFTSCT-UHFFFAOYSA-N 0.000 description 1
- OKBVMLGZPNDWJK-UHFFFAOYSA-N Nc(c1c2cccc1)ccc2N Chemical compound Nc(c1c2cccc1)ccc2N OKBVMLGZPNDWJK-UHFFFAOYSA-N 0.000 description 1
- HBJPJUGOYJOSLR-UHFFFAOYSA-N Nc1cc2cc(N)ccc2cc1 Chemical compound Nc1cc2cc(N)ccc2cc1 HBJPJUGOYJOSLR-UHFFFAOYSA-N 0.000 description 1
- OAOXYBSWOZWDBB-UHFFFAOYSA-N O=P(c1ccccc1)(c1ccccc1)c(cc1)cc(cc2)c1cc2-c1cc2ccc(cccn3)c3c2nc1 Chemical compound O=P(c1ccccc1)(c1ccccc1)c(cc1)cc(cc2)c1cc2-c1cc2ccc(cccn3)c3c2nc1 OAOXYBSWOZWDBB-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SXCQOWSCNMKTFA-UHFFFAOYSA-N phosphorosobenzene Chemical group O=PC1=CC=CC=C1 SXCQOWSCNMKTFA-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
Definitions
- the invention relates to an alcohol-soluble cathode buffer layer material, in particular to an ion-type cathode buffer layer molecular type material, a preparation method and application thereof.
- Inverted organic optoelectronic devices can avoid the use of low work function metals as cathodes, which is beneficial to improve device stability. Therefore, it is important to apply cathode buffer materials for inverted optoelectronic devices.
- the organic small molecule cathode interface material has the advantages of certain chemical structure, high purity, excellent synthesis and purification repeatability, and has a very good application in the conventional organic photoelectric device.
- most of the organic small molecule cathode interface materials are difficult to resist the erosion of weak polar solvents, that is, they are easily and partially washed away when the active layer is spin-coated, and the application in the inverted structure organic photoelectric device is limited. Therefore, it is particularly urgent to design and synthesize organic small molecule cathode interface materials with the ability to resist weak polar solvent erosion.
- an object of the present invention to provide an ion-type cathode buffer layer molecular type material which is resistant to corrosion by a weakly polar solvent.
- Another object of the present invention is to provide a method for preparing the above-described ion-type cathode buffer layer molecular type material.
- a third object of the present invention is to provide an application of the above-described ion-type cathode buffer layer molecular type material.
- the ionic cathode buffer layer molecular type material has the following chemical structural formula:
- the alkyl ion-containing counter ion directly connected to the root ion, when n 1, R 3 , R 4 , and R 5 are alkyl chains having 1 to 18 carbon atoms, and X ⁇ is an anion;
- the ionic cathode buffer layer molecular type material has the following chemical structural formula:
- R 1 is an aryl group or a fused ring aryl group
- R 2 is a nitrogen heterocyclic ring and an ionic salt has been formed
- the R 1 is any one of the following structural units:
- R 6 and R 7 are selected from an alkyl chain or an alkoxy chain having 1 to 18 carbon atoms or are any of the following structural units:
- R8 and R9 are alkyl chains having 1 to 18 carbon atoms.
- the R 2 is any one of the following structural units:
- R 3 and R 4 are alkyl chains having 1 to 18 carbon atoms, and R 5 is any one of the following structural units:
- the preparation method of the ionic cathode buffer layer molecular type material comprises the following steps:
- the group R 2 is first reacted with an alkyl chain having a bromine group at both ends to obtain a target product having a bromine group at one end of the alkyl chain, and then reacted with an alkyl chain containing a secondary amine to obtain a target product;
- the target product containing the boronic acid ester obtained in the step (2) is reacted with a nitrogen-containing heterocyclic ring containing a bromine to obtain a neutral target product;
- the ionic salt of the bromine obtained by the step 6) is ion-exchanged with the sodium salt of the target anion to obtain a molecular type material containing the ionic cathodic buffer layer.
- ionic cathode buffer layer molecular type material in an organic photovoltaic cell device, an electroluminescent display, illumination or an organic field effect transistor.
- the organic small molecule cathode interface material is difficult to resist the erosion of the weak polar solvent, that is, it is easy to be partially or completely washed away when the active layer is spin-coated, and the application in the inverted structure organic photovoltaic cell device is limited.
- the present invention reduces the solubility in a weakly polar solvent (for example, toluene, chlorobenzene) by lowering the solubility in a weakly polar solvent by using an amine group or a nitrogen heterocyclic group to form an ionic salt; Phenyl phosphorus oxide group, improving the alcohol solubility and solution processing properties of the material.
- a weakly polar solvent for example, toluene, chlorobenzene
- the present invention has the following advantages and benefits:
- the ionic cathode buffer layer molecular type material of the present invention can reduce the solubility (for example, toluene, chlorobenzene) in a weakly polar solvent, resists the attack of a weakly polar solvent, and can resist the corrosion of a weakly polar solvent.
- solubility for example, toluene, chlorobenzene
- the ionic cathode buffer layer molecular type material of the invention has good alcohol solubility and solution addition Performance.
- the ion-type cathode buffer layer molecular type material of the present invention has good film morphology stability.
- 1a and 1b are differential scanning calorimetry curves of an ion-type cathode buffer layer molecular type material POBiNa-Z and PONaPhen-Br, respectively, according to an embodiment of the present invention.
- 3 is a current density-voltage curve of an organic photovoltaic cell device in which the cathodes are ZnO/POBiNa-Z, ZnO/PONaPhen-Br, and ZnO, respectively.
- 2,6-dibromonaphthalene (3g, 10.5mmol) was dissolved in dry tetrahydrofuran (200mL) cooled to -78 °C.
- n-Butyllithium (2.4 M solution in hexane, 4.8 mL, 11.55 mmol) was added dropwise via a syringe. Stirring was carried out for 40 minutes under a N 2 atmosphere at this temperature, then diphenylphosphine chloride (2.3 mL, 12.6 mmol) was added by syringe. The mixture was slowly returned to room temperature and stirring was continued overnight under N 2 atmosphere.
- 1,1'-bisdiphenylphosphinoferrocene palladium dichloride 80 mg, 0.11 mmol was added to compound 2 (1.35 g, 3.32 mmol) and boranoic acid pinacol ester (1.26) under N 2 atmosphere. g, 4.98 mmol), a mixture of potassium acetate (977 mg, 9.95 mmol) and N,N-dimethylformamide (30 mL). The reaction was heated to 80 ° C and allowed to react for 2 hours. After cooling to room temperature, dichloromethane and distilled water were added to the reaction mixture, and the organic layer was separated, and the aqueous layer was extracted with dichloromethane.
- 2,6-dibromonaphthalene (3g, 10.5mmol) was dissolved in dry tetrahydrofuran (200mL) cooled to -78 °C.
- n-Butyllithium (2.4 M solution in hexane, 4.8 mL, 11.55 mmol) was added dropwise via a syringe. Stirring was carried out for 40 minutes under a N 2 atmosphere at this temperature, then diphenylphosphine chloride (2.3 mL, 12.6 mmol) was added by syringe. The mixture was slowly returned to room temperature and stirring was continued overnight under N 2 atmosphere.
- 1,1'-bisdiphenylphosphinoferrocene palladium dichloride 80 mg, 0.11 mmol was added to compound 2 (1.35 g, 3.32 mmol) and boranoic acid pinacol ester (1.26) under N 2 atmosphere. g, 4.98 mmol), a mixture of potassium acetate (977 mg, 9.95 mmol) and N,N-dimethylformamide (30 mL). The reaction was heated to 80 ° C and allowed to react for 2 hours. After cooling to room temperature, dichloromethane and distilled water were added to the reaction mixture, and the organic layer was separated, and the aqueous layer was extracted with dichloromethane.
- DSC Differential Scanning Calorimetry
- the ion-type cathode buffer layer molecular materials of Examples 1 to 2 were tested against weak polar solvent erosion:
- the solubility of the cathode interface material in a weakly polar solvent was tested.
- the solubility of both POBiNa-Z and PONaPhen-Br in toluene and chlorobenzene solvents was less than 0.1 mg mL -1 (insoluble), of which PONaPhen-Br even
- the solubility in chloroform is also less than 0.1 mg mL -1 , indicating that it is well resistant to solvent solvent attack.
- the resistance of the cathode interface material to weakly polar solvents was investigated by comparing the UV-Vis absorption spectra.
- weakly polar solvents for example, toluene, chlorobenzene
- a chloroform solution was spin-coated on a quartz plate at a concentration of 10 mg mL -1 , a rotation speed of 2000 rpm, an annealing at 100 ° C for 10 min, and a toluene or chlorobenzene solvent was spin-coated on the surface of the film.
- weakly polar solvents for example, toluene, chlorobenzene
- A is the absorbance
- I 0 is the incident light intensity
- I is the transmitted light intensity after passing the sample
- ⁇ is the molar absorptivity
- l is the sample thickness
- c is the sample concentration
- ⁇ and c are fixed for the same sample. Therefore, the absorption strength of the film is proportional to the thickness of the film, and the ability of the cathode interface material to resist solvent erosion is judged by comparing the change in the absorption strength of the film before and after spin-coating of the toluene or chlorobenzene solvent. As shown in Figure 2, POBiNa-Z resists the attack of toluene and chlorobenzene.
- POBiNa-Z and PONaPhen-Br were selected as the cathode interface materials, and PTB7:PC 71 BM was used as the active layer material.
- the specific preparation process was as follows:
- ITO indium tin oxide
- a methanol solution of POBiNa-Z and PONaPhen-Br was spin-coated on the surface of ZnO at a concentration of 0.75 mg mL -1 at a rotation speed of 2000 rpm and annealed at 100 ° C for 10 minutes.
- a solution of PTB7:PC 71 BM in chlorobenzene was spin-coated on the cathode interface layer to a thickness of about 100 nm (concentration: 10:15 mg mL -1 , rotation speed of 1500 rpm, time 30 s), and pumped under vacuum for 4 h.
- MoO 3 is evaporated under a vacuum of ⁇ 5 ⁇ 10 -4 Pa (the evaporation rate is ), the thickness is 10 nm.
- a device containing only ZnO is used as a comparison device, and the specific device structure is as follows:
- ITO/ZnO/POBiNa-Z/PTB7 PC 71 BM/MoO 3 /Al
- ITO/ZnO/PONaPhen-Br/PTB7 PC 71 BM/MoO 3 /Al
- ITO/ZnO/PTB7 PC 71 BM/MoO 3 /Al
- the energy conversion efficiency of the organic photovoltaic cell device prepared by the solution processing method was significantly improved by using POBiNa-Z and PONaPhen-Br.
- the energy conversion efficiencies are 7.54% and 7.59%, respectively, which is 4% higher than that of pure ZnO devices, and the current density and fill factor are improved, indicating that the cathode buffer layer material can be modified.
- the cathode facilitates electron extraction and improves device performance.
- Table 1 Preliminary characterization results of organic photovoltaic cell devices with cathodes of ZnO/POBiNa-Z and ZnO, respectively
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Abstract
本发明公开了离子型阴极缓冲层分子型材料，将芳基磷氧基团引入到铵根离子盐中，不仅具有较高的醇溶性及非晶态特性，还可以降低在弱极性溶剂中的溶解度，抵御弱极性溶剂的侵蚀。本发明还公开上了上述离子型阴极缓冲层分子型材料的制备方法和应用。相比于现有的有机小分子阴极缓冲层材料，本发明的离子型阴极缓冲层分子型材料适合于"多层"溶液加工倒置器件结构中的应用。
Description
本发明涉及醇溶性阴极缓冲层材料，特别涉及一种离子型阴极缓冲层分子型材料及其制备方法和应用。
倒置结构的有机光电器件可避免使用低功函的金属作为阴极，有利于提高器件稳定性，因此，可适用于倒置光电器件的阴极缓冲层材料具有重要意义。
有机小分子阴极界面材料具有确定的化学结构、高纯度以及优良的合成、提纯重复性等优点，在传统有机光电器件中有非常好的应用。然而，大部分有机小分子阴极界面材料很难抵御弱极性溶剂的侵蚀，即旋涂活性层时易被部分或完全洗去，在倒置结构的有机光电器件中的应用受到了一定的限制。因此，设计、合成具有抵御弱极性溶剂侵蚀能力的有机小分子阴极界面材料显得尤为迫切。
发明内容
为了克服现有技术的上述缺点与不足，本发明的目的之一在于提供一种离子型阴极缓冲层分子型材料，可抵御弱极性溶剂的腐蚀。
本发明的目的之二在于提供上述离子型阴极缓冲层分子型材料的制备方法。
本发明的目的之三在于提供上述离子型阴极缓冲层分子型材料的应用。
本发明的目的通过以下技术方案实现：
离子型阴极缓冲层分子型材料，具有如下化学结构式：
其中，R1，R2为芳基或稠环芳基，m＝0～17，当n＝0时，R3、R4为碳数为1～18的烷基链，R5为与铵根离子直接相连的含烷基链的反离子，当n＝1时，R3、R4、R5为碳数为1～18的烷基链，X–是阴离子；
或者，离子型阴极缓冲层分子型材料具有如下化学结构式：
其中，R1为芳基或稠环芳基；R2为氮杂环，并已形成离子盐；当n＝0时，氮杂环通过烷基链与反离子直接相连，当n＝1时，氮杂环上连接碳数为1–18的烷基链，X–是阴离子，r＝1～2。
所述R1为如下结构单元的任一种：
其中，R6，R7从碳数为1–18的烷基链或烷氧基链中选择或为如下结构单元的任一种：
其中，R8，R9为碳数为1～18的烷基链。
所述R2为如下结构单元的任一种：
当n＝0时，R3、R4为碳数为1～18的烷基链，所述R5为如下结构单元的任一种：
当n＝1时，所述X–具有如下结构单元中的一种：
所述的离子型阴极缓冲层分子型材料的制备方法，包括以下步骤：
(1)以氯化二苯基膦作为反应原料，通过正丁基锂低温反应引入到基团R1上，再通过双氧水氧化得到含溴的已氧化的目标产物，其中，对于R6，R7，可
通过甲烷磺酸对芴酮进行催化引入芳基、稠环芳基，或通过氢氧化钾对芴进行催化引入碳数为1～18的烷基链或烷氧基链；
(2)以步骤(1)所得的含溴的已氧化的目标产物，通过钯催化剂的作用，与联硼酸频那醇酯反应，得到含硼酸酯的目标产物；
(3)基团R2作为反应原料，通过与含叔胺的且一端带氯的烷基链反应，得到含胺基的目标产物；
或者，基团R2先通过碳酸钾与两端带溴的烷基链反应，得到烷基链一端带溴的目标产物，再通过碳酸钾与含有仲胺的烷基链反应得到目标产物；
(4)以步骤(2)所得的含硼酸酯的目标产物与步骤(3)所得的目标产物，通过钯催化偶联反应，得到同时含有磷氧基团及胺基的目标产物；
或者，以步骤(2)所得的含硼酸酯的目标产物与含溴的氮杂环反应，得到中性的目标产物；
当n＝0时，步骤(4)之后进行以下步骤：
(5)以步骤(4)所得的目标产物，通过与1,3-磺内酯反应，得到离子型阴极缓冲层分子型材料；
当n＝1时，步骤(4)之后进行以下步骤：
(6)以步骤(4)所得的目标产物，通过与溴烃烷反应，得到阴离子为溴离子的目标产物；
(7)以步骤6)所得的阴离子为溴的离子盐，通过与目标阴离子的钠盐进行离子交换，得到含有离子型阴极缓冲层分子型材料。
所述的离子型阴极缓冲层分子型材料的在有机光伏电池器件、电致发光显示、照明或有机场效应晶体管中的应用。
本发明的原理如下：
有机小分子阴极界面材料很难抵御弱极性溶剂的侵蚀，即旋涂活性层时易被部分或完全洗去，在倒置结构的有机光伏电池器件中的应用受到了一定的限制。本发明通过将胺基基团或者氮杂环基团形成离子盐，降低在弱极性溶剂中的溶解度(例如，甲苯、氯苯)，以低于弱极性溶剂的侵蚀；同时，引入二苯基磷氧基团，改善材料的醇溶性及溶液加工性能。
与现有技术相比，本发明具有以下优点和有益效果：
(1)本发明的离子型阴极缓冲层分子型材料可以降低在弱极性溶剂中的溶解度(例如，甲苯、氯苯)，抵御弱极性溶剂的侵蚀，可抵御弱极性溶剂的腐蚀。
(2)本发明的离子型阴极缓冲层分子型材料，具有较好的醇溶性及溶液加
工性能。
(3)本发明的离子型阴极缓冲层分子型材料，具有良好的薄膜形貌稳定性。
图1a和图1b分别为本发明的实施例的离子型阴极缓冲层分子型材料POBiNa-Z和PONaPhen-Br的差示扫描量热曲线。
图2为以石英片为基底的POBiNa-Z薄膜的溶剂洗涤前后的吸收光谱。
图3为阴极分别为ZnO/POBiNa-Z、ZnO/PONaPhen-Br、ZnO的有机光伏电池器件的电流密度-电压曲线。
下面结合实施例，对本发明作进一步地详细说明，但本发明的实施方式不限于此。
实施例1
本实施例中的离子型阴极缓冲层分子型材料结构式如下：
本实施例的离子型阴极缓冲层分子型材料的制备过程如下：
步骤一：(2-溴-6-萘基)二苯基膦(1)的制备
在N2气氛下，将2,6-二溴萘(3g,10.5mmol)溶于干燥的四氢呋喃(200mL)中，冷却到–78℃。通过注射器滴加入正丁基锂(2.4M solution in hexane,4.8mL,11.55mmol)。在N2气氛及该温度下搅拌40分钟，然后氯化二苯基膦(2.3mL,12.6mmol)通过注射器加入。混合液慢慢恢复到室温，在N2气氛下继续搅拌过夜。待反应结束，加入少量乙醇终止反应，减压蒸馏除去四氢呋喃后，用二氯甲烷溶解，加入蒸馏水并用二氯甲烷萃取。有机层用无水硫酸镁干燥，过滤，减压
蒸馏除去溶剂后用硅胶柱分离，洗脱剂为石油醚和二氯甲烷的混合溶剂(4:1v/v)，得到白色固体，产率81％(3.3g)。
步骤二，(2-溴-6-萘基)二苯基氧化膦(2)的制备
向化合物1(2.7g,7.23mmol)的二氯甲烷(30mL)溶液中加入双氧水(30％,10mL)。反应在室温下搅拌过夜。待反应结束，向反应混合物中加入亚硫酸氢钠水溶液以还原过量的双氧水，并用二氯甲烷萃取。有机层用无水硫酸镁干燥，过滤，减压蒸馏除去溶剂后用硅胶柱分离，洗脱剂为二氯甲烷和乙酸乙酯的混合溶剂(4:1v/v)，得到白色固体，产率96％(2.7g)。1H NMR(300MHz,DMSO,ppm):δ7.53–7.60(m,4H),7.62–7.77(m,8H),8.03–8.08(m,2H),8.33(s,1H),8.36(d,1H,J＝13.86Hz).
步骤三，(2-(4,4,5,5-四甲基-2-1,3,2–二氧杂硼烷基)-6-萘基)二苯基氧化膦(3)的制备
在N2气氛下，将1,1’-双二苯基膦二茂铁二氯化钯(80mg,0.11mmol)加入到化合物2(1.35g,3.32mmol)、联硼酸频那醇酯(1.26g,4.98mmol)、醋酸钾(977mg,9.95mmol)与N,N-二甲基甲酰胺(30mL)的混合液中。反应加热到80℃并反应2小时。待冷却到室温，向反应混合物中加入二氯甲烷和蒸馏水并分离有机层，再用二氯甲烷萃取水层。合并有机层后，用水洗涤三次，再用无水硫酸镁干燥，过滤，减压蒸馏除去溶剂后用硅胶柱分离，洗脱剂为二氯甲烷和乙酸乙酯的混合溶剂(3:1v/v)，得到白色固体，产率83％(1.25g)。1H NMR(300MHz,DMSO,ppm):δ1.34(s,12H),7.53–7.71(m,11H),7.79(d,1H,J＝8.2Hz),8.05(d,1H,J＝8.4Hz),8.16(d,1H,J＝13.7Hz),8.39(s,1H).
步骤四，3-(2-溴-6-萘氧基)-N,N-二甲基-1-丙基胺(4)的制备
将2-溴-6-萘酚(3g,13.45mmol)、碳酸铯(17.5g,53.8mmol)和乙腈(80mL)的混合液在N2气氛下加热回流反应30分钟后，向反应体系中加入N,N-二甲氨基-3-氯丙烷(盐酸盐)(2.76g,17.48mmol)，继续加热回流搅拌24h。待冷却至室温，向反应混合物中加入蒸馏水，并用二氯甲烷萃取。有机层用无水硫酸镁干燥，过滤，减压蒸馏除去溶剂后用硅胶柱分离，洗脱剂为二氯甲烷和乙醇的混合溶剂(20:1v/v)，得到白色固体，产率82％(3.4g)。1H NMR(300MHz,DMSO,ppm):δ1.86–1.95(m,2H),2.16(s,6H),2.39(t,2H,J＝7.05Hz),4.11(t,2H,J＝6.48Hz),7.23(dd,1H,J＝8.91,2.54Hz),7.36(s,1H),7.58(dd,1H,J＝8.70,2.10Hz),7.83(t,2H,J＝9.23Hz),8.11(s,1H).
步骤五，3-(2-(2-(二苯基磷氧基)-6-萘基)-6-萘氧基)-N,N-二甲基-1-丙基胺(5)的制备
在N2气氛下，将醋酸钯(10mg,0.04mmol)、三环己基膦(25mg,0.09mmol)加入到(2-(4,4,5,5-四甲基-2-1,3,2–二氧杂硼烷基)-6-萘基)二苯基氧化膦(1g,2.20mmol)、化合物4(563mg,1.83mmol)、碳酸钠水溶液(2M,4mL,8mmol)、甲苯(25mL)和乙醇(4mL)的混合液中。反应加热到90℃并搅拌过夜。待冷却到室温，向反应混合物中加入蒸馏水并分离甲苯层，再用二氯甲烷萃取水层。有机层用无水硫酸镁干燥，过滤，减压蒸馏除去溶剂后用硅胶柱分离，洗脱剂为二氯甲烷和乙醇的混合溶剂(20:1v/v)，得到白色固体，产率61％(320mg)。1H NMR(400MHz,DMSO,ppm):δ1.94(t,2H,J＝6.70Hz),2.20(s,6H),2.45(t,2H,J＝7.02Hz),4.15(t,2H,J＝6.34Hz),7.23(d,1H,J＝8.92Hz),7.38(s,1H),7.56–7.73(m,11H),7.94–7.97(m,3H),8.11(d,1H,J＝8.64Hz),8.14–8.19(m,2H),8.33–8.35(m,2H),8.44(s,1H).
步骤六，化合物POBiNa-Z的制备
向化合物5(550mg,0.99mmol)的甲苯(20ml)溶液中加入1,3-丙烷磺内酯(242mg,1.98mmol)，在N2气氛下加热回流搅拌2天。冷却到室温，向反应混合物中加入碳酸氢钠水溶液并充分搅拌，再分离甲苯层，并用二氯甲烷萃取水层。合并有机层后，用水洗涤三次，再用无水硫酸镁干燥，过滤，减压蒸馏除去溶剂后三氧化二铝柱子分离，洗脱剂为二氯甲烷和甲醇的混合溶剂(10:1v/v)，最后用正己烷重结晶并过滤得到白色产品，产率30％(200mg)。1H NMR(400MHz,CD3OH,ppm):δ2.27(m,2H),2.37(m,2H),2.90(m,2H),3.17(s,6H),3.61–3,62(m,4H),4.26(m,2H),7.24(d,2H,J＝8.72Hz),7.32(s,1H),7.58–7.74(m,11H),7.89(m,3H),8.01(m,2H),8.10(d,2H,J＝8.28Hz),8.19–8.23(m,2H),8.28(s,1H).
实施例2
本实施例中的离子型阴极缓冲层分子型材料结构式如下：
本实施例的离子型阴极缓冲层分子型材料的制备过程如下：
步骤一：(2-溴-6-萘基)二苯基膦(1)的制备
在N2气氛下，将2,6-二溴萘(3g,10.5mmol)溶于干燥的四氢呋喃(200mL)中，冷却到–78℃。通过注射器滴加入正丁基锂(2.4M solution in hexane,4.8mL,11.55mmol)。在N2气氛及该温度下搅拌40分钟，然后氯化二苯基膦(2.3mL,12.6mmol)通过注射器加入。混合液慢慢恢复到室温，在N2气氛下继续搅拌过夜。
待反应结束，加入少量乙醇终止反应，减压蒸馏除去四氢呋喃后，用二氯甲烷溶解，加入蒸馏水并用二氯甲烷萃取。有机层用无水硫酸镁干燥，过滤，减压蒸馏除去溶剂后用硅胶柱分离，洗脱剂为石油醚和二氯甲烷的混合溶剂(4:1v/v)，得到白色固体，产率81％(3.3g)。
步骤二，(2-溴-6-萘基)二苯基氧化膦(2)的制备
向化合物1(2.7g,7.23mmol)的二氯甲烷(30mL)溶液中加入双氧水(30％,10mL)。反应在室温下搅拌过夜。待反应结束，向反应混合物中加入亚硫酸氢钠水溶液以还原过量的双氧水，并用二氯甲烷萃取。有机层用无水硫酸镁干燥，过滤，减压蒸馏除去溶剂后用硅胶柱分离，洗脱剂为二氯甲烷和乙酸乙酯的混合溶剂(4:1v/v)，得到白色固体，产率96％(2.7g)。1H NMR(300MHz,DMSO,ppm):δ7.53–7.60(m,4H),7.62–7.77(m,8H),8.03–8.08(m,2H),8.33(s,1H),8.36(d,1H,J＝13.86Hz).
步骤三，(2-(4,4,5,5-四甲基-2-1,3,2–二氧杂硼烷基)-6-萘基)二苯基氧化膦(3)的制备
在N2气氛下，将1,1’-双二苯基膦二茂铁二氯化钯(80mg,0.11mmol)加入到化合物2(1.35g,3.32mmol)、联硼酸频那醇酯(1.26g,4.98mmol)、醋酸钾(977mg,9.95mmol)与N,N-二甲基甲酰胺(30mL)的混合液中。反应加热到80℃并反应2小时。待冷却到室温，向反应混合物中加入二氯甲烷和蒸馏水并分离有机层，再用二氯甲烷萃取水层。合并有机层后，用水洗涤三次，再用无水硫酸镁干燥，过滤，减压蒸馏除去溶剂后用硅胶柱分离，洗脱剂为二氯甲烷和乙酸乙酯的混合溶剂(3:1v/v)，得到白色固体，产率83％(1.25g)。1H NMR(300MHz,DMSO,ppm):δ1.34(s,12H),7.53–7.71(m,11H),7.79(d,1H,J＝8.2Hz),8.05(d,1H,J＝8.4Hz),8.16(d,1H,J＝13.7Hz),8.39(s,1H).
步骤四，(2-(3-1,10-菲啰啉基)-6-萘基)二苯基氧化膦(6)的制备
在N2气氛下，将醋酸钯(4.5mg,0.02mmol)、三环己基膦(11.2mg,0.04mmol)加入到化合物3(289mg,0.64mmol)、3-溴-1,10-菲啰啉(150mg,0.58mmol)、碳酸钠水溶液(2M,2mL,4mmol)、甲苯(30mL)和乙醇(8mL)的混合液中。反应加热到90℃并搅拌过夜。待冷却到室温，向反应混合物中加入蒸馏水并分离甲苯层，再用二氯甲烷萃取水层。有机层用无水硫酸镁干燥，过滤，减压蒸馏除去溶剂后用硅胶柱分离，洗脱剂为二氯甲烷和乙醇的混合溶剂(20:1v/v)，得到白色固体，产率68％(200mg)。1H NMR(300MHz,DMSO,ppm):δ7.56–7.81(m,12H),8.04–8.12(m,2H),8.21–8.31(m,3H),8.44(d,1H,J＝13.5Hz),8.53(dd,1H,J＝8.1,1.7Hz),8.67(s,1H),8.99(s,1H),9.14(dd,1H,J＝4.3,1.7Hz),9.62(s,1H).
步骤五，化合物PONaPhen-Br的制备
在N2气氛下，将(2-(3-1,10-菲啰啉基)-6-萘基)二苯基氧化膦(100mg,0.20mmol)溶解于1,2-二溴乙烷(5mL)中，在温度110℃下加热回流过夜。待有黄色固体析出，用二氯甲烷重结晶，得到黄色固体，产率66％(90mg)。1H NMR(400MHz,CD3OH):δ10.43(s,1H),10.05(s,1H),9.77(d,1H,J＝7.52Hz),9.61(d,1H,J＝11.36Hz),8.76–8.84(m,3H),8.67(t,1H,J＝9.42Hz),8.30–8.42(m,4H),7.62–7.89(m,11H),5.84(d,4H,J＝8.8Hz)ppm.
测试例：
对实施例1～2的离子型阴极缓冲层分子型材料进行醇溶解度测试：
对POBiNa-Z和PONaPhen-Br进行了定量的溶解性实验。在室温下，在甲醇中的溶解度分别为10mg mL-1和4mg mL-1；而在Chem.Asian J.2012,7,2126-2132,Liu et al.中报道的含有线性共轭单元的阴极缓冲层材料2b，加热情况
下，即使在甲醇中的溶解度约为或小于2mg mL-1。
对实施例1～2的离子型阴极缓冲层分子型材料进行热学性质测试：
差示扫描量热分析(DSC)是在NETZSCH DSC 204 F1热分析仪测得，升温速率为10℃/min，并以氮气为保护气。
如图1a和图1b，差示扫描量热分析表明，在第一轮、第二轮加热以及降温过程中，POBiNa-Z和PONaPhen-Br均没有出现熔融峰和结晶峰，并表现出明显的玻璃化转变，对应的玻璃化转变温度为分别为145℃和133℃。这表明材料可以形成稳定的无定形态。
对实施例1～2的离子型阴极缓冲层分子型材料进行抵御弱极性溶剂侵蚀能力测试：
首先测试阴极界面材料在弱极性溶剂中的溶解度，POBiNa-Z和PONaPhen-Br均在甲苯、氯苯溶剂中的溶解度均小于0.1mg mL-1(难溶)，其中，PONaPhen-Br甚至在氯仿中的溶解度也小于0.1mg mL-1，表明其可很好的抵御溶剂型溶剂的侵蚀。
随后，通过对比紫外-可见吸收光谱来研究阴极界面材料对弱极性溶剂(例如，甲苯、氯苯)的抵御能力。以POBiNa-Z为例，将其氯仿溶液旋涂在石英片上，浓度为10mg mL–1，转速为2000rpm，100℃退火10min，再将甲苯或氯苯溶剂旋涂在该薄膜表面。根据朗伯-比尔定律，
其中，A表示吸光度，I0为入射光强度，I为通过样品后透射光强度，ε表示摩尔吸光系数，l表示样品厚度，c表示样品浓度，对于同一样品，ε和c均固定不变，因此，薄膜的吸收强度与该薄膜厚度成正比，通过对比旋涂甲苯或氯苯溶剂前后的薄膜吸收强度的变化，判断阴极界面材料抵御溶剂侵蚀的能力。如图2所示，POBiNa-Z可以抵御甲苯、氯苯的侵蚀。
实施例1～2采用溶液加工法的有机光伏电池器件的制备过程与表征结果：
选用POBiNa-Z和PONaPhen-Br作为阴极界面材料，采用PTB7:PC71BM作为活性层材料，具体制备过程如下：
首先将电阻为15Ωsquare–1的氧化铟锡(ITO)导电玻璃片依次经去离子水、丙酮、洗涤剂、去离子水和异丙醇通过超声清洗，每步各20min。在烘箱中烘干后，在ITO玻璃片上，旋涂ZnO(溶胶-凝胶法)，厚度30–40nm，转速为4000rpm，200℃退火1h。然后，在ZnO表面旋涂POBiNa-Z和PONaPhen-Br的甲
醇溶液，浓度为0.75mg mL–1，转速为2000rpm，100℃退火10min。将PTB7:PC71BM的氯苯溶液旋涂在阴极界面层上，厚度约为100nm(浓度为10:15mg mL–1,转速为1500rpm，时间为30s)，在真空下抽4h。在<5×10-4Pa的真空下，将蒸镀MoO3(蒸镀速率为
)，厚度为10nm。最后，在<5×10-4Pa的真空下，蒸镀金属Al。PTB7:PC71BM器件的有效发光面积为0.16cm2。除ZnO薄膜的制备过程是在大气环境中完成的，其余所有环节均在氮气气氛的手套箱内完成。
采用仅含有ZnO的器件作为对比器件，具体器件结构如下：
器件I：ITO/ZnO/POBiNa-Z/PTB7:PC71BM/MoO3/Al
器件II：ITO/ZnO/PONaPhen-Br/PTB7:PC71BM/MoO3/Al
器件III：ITO/ZnO/PTB7:PC71BM/MoO3/Al
如表1及图3所示，以溶液加工法制备的有机光伏电池器件，采用POBiNa-Z和PONaPhen-Br后，能量转化效率明显提高。例如，在有机光伏电池器件中，能量转化效率分别为7.54％和7.59％，相比于纯ZnO器件，提高了4％，电流密度和填充因子均有所提高，表明该阴极缓冲层材料能修饰阴极，有利于电子抽取，改善器件性能。
表1：阴极分别为ZnO/POBiNa-Z、ZnO的有机光伏电池器件的初步表征结果
[a]光强：100mW cm-2。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受所述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (7)
- 离子型阴极缓冲层分子型材料，其特征在于，具有如下化学结构式：
其中，R1，R2为芳基或稠环芳基，m＝0～17，当n＝0时，R3、R4为碳数为1–18的烷基链，R5为与铵根离子直接相连的含烷基链的反离子，当n＝1时，R3、R4、R5为碳数为1～18的烷基链，X–是阴离子；或者，离子型阴极缓冲层分子型材料具有如下化学结构式：
其中，R1为芳基或稠环芳基；R2为氮杂环，并已形成离子盐；当n＝0时，氮杂环通过烷基链与反离子直接相连，当n＝1时，氮杂环上连接碳数为1～18的烷基链，X–是阴离子，r＝1～2。 - 根据权利要求1所述的离子型阴极缓冲层分子型材料，其特征在于，所述R1为如下结构单元的任一种：
其中，R6，R7从碳数为1–18的烷基链或烷氧基链中选择或为如下结构单元的任一种：
其中，R8，R9为碳数为1～18的烷基链。 - 根据权利要求1所述的离子型阴极缓冲层分子型材料，其特征在于，所 述R2为如下结构单元的任一种：
- 根据权利要求1所述的离子型阴极缓冲层分子型材料，其特征在于，当n＝0时，R3、R4为碳数为1～18的烷基链，所述R5为如下结构单元的任一种：
- 根据权利要求1所述的离子型阴极缓冲层分子型材料，其特征在于，当n＝1时，所述X–具有如下结构单元中的一种：
- 权利要求1所述的离子型阴极缓冲层分子型材料的制备方法，其特征在于，包括以下步骤：(1)以氯化二苯基膦作为反应原料，通过正丁基锂低温反应引入到基团R1上，再通过双氧水氧化得到含溴的已氧化的目标产物，其中，对于R6，R7，可通过甲烷磺酸对芴酮进行催化引入芳基、稠环芳基，或通过氢氧化钾对芴进行催化引入碳数为1～18的烷基链或烷氧基链；(2)以步骤(1)所得的含溴的已氧化的目标产物，通过钯催化剂的作用，与联硼酸频那醇酯反应，得到含硼酸酯的目标产物；(3)基团R2作为反应原料，通过与含叔胺的且一端带氯的烷基链反应，得到含胺基的目标产物；或者，基团R2先通过碳酸钾与两端带溴的烷基链反应，得到烷基链一端带溴的目标产物，再通过碳酸钾与含有仲胺的烷基链反应得到目标产物；(4)以步骤(2)所得的含硼酸酯的目标产物与步骤(3)所得的目标产物，通过钯催化偶联反应，得到同时含有磷氧基团及胺基的目标产物；或者，以步骤(2)所得的含硼酸酯的目标产物与含溴的氮杂环反应，得到中性的目标产物；当n＝0时，步骤(4)之后进行以下步骤：(5)以步骤(4)所得的目标产物，通过与1,3-磺内酯反应，得到离子型阴极缓冲层分子型材料；当n＝1时，步骤(4)之后进行以下步骤：(6)以步骤(4)所得的目标产物，通过与溴烃烷反应，得到阴离子为溴离子的目标产物；(7)以步骤6)所得的阴离子为溴的离子盐，通过与目标阴离子的钠盐进行离子交换，得到含有离子型阴极缓冲层分子型材料。
- 权利要求1～5任一项所述的离子型阴极缓冲层分子型材料的在有机光伏电池器件、电致发光显示、照明或有机场效应晶体管中的应用。
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