CN113675349A - Composite hole transport material and organic electroluminescent element - Google Patents
Composite hole transport material and organic electroluminescent element Download PDFInfo
- Publication number
- CN113675349A CN113675349A CN202010415242.2A CN202010415242A CN113675349A CN 113675349 A CN113675349 A CN 113675349A CN 202010415242 A CN202010415242 A CN 202010415242A CN 113675349 A CN113675349 A CN 113675349A
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- Prior art keywords
- compound
- hole transport
- layer
- transport material
- composite
- Prior art date
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- Pending
Links
- 230000005525 hole transport Effects 0.000 title claims abstract description 88
- 239000000463 material Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims description 36
- 238000002347 injection Methods 0.000 claims description 25
- 239000007924 injection Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 16
- 230000000903 blocking effect Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 239000011368 organic material Substances 0.000 claims description 9
- 238000000859 sublimation Methods 0.000 claims description 8
- 230000008022 sublimation Effects 0.000 claims description 8
- 230000006872 improvement Effects 0.000 claims description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 126
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- -1 Ca/Ag Chemical class 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 229940126062 Compound A Drugs 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WACBNQHQGKZXMF-UHFFFAOYSA-N 2'-bromo-2-chloro-9,9'-spirobi[fluorene] Chemical compound C1=CC=C2C(=C1)C3=C(C24C5=CC=CC=C5C6=C4C=C(C=C6)Br)C=C(C=C3)Cl WACBNQHQGKZXMF-UHFFFAOYSA-N 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- BZHGXQBPJUHVFW-UHFFFAOYSA-N toluene;tritert-butylphosphane Chemical compound CC1=CC=CC=C1.CC(C)(C)P(C(C)(C)C)C(C)(C)C BZHGXQBPJUHVFW-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 238000000151 deposition Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- WSHZWUXRWQVZQP-UHFFFAOYSA-N 1-bromo-2-(4-chlorophenyl)benzene Chemical group C1=CC(Cl)=CC=C1C1=CC=CC=C1Br WSHZWUXRWQVZQP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- HKRVHTFXSUGWIV-UHFFFAOYSA-N 1,1'-spirobi[fluorene]-2'-amine Chemical class C12=CC3=CC=CC=C3C1=CC=CC12C2=CC3=CC=CC=C3C2=CC=C1N HKRVHTFXSUGWIV-UHFFFAOYSA-N 0.000 description 1
- IOQMWOBRUDNEOA-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzonitrile Chemical compound FC1=CC(F)=C(F)C(C#N)=C1F IOQMWOBRUDNEOA-UHFFFAOYSA-N 0.000 description 1
- QFUPJXCUNNWZJQ-UHFFFAOYSA-N 2-bromofluoren-1-one Chemical compound C1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 QFUPJXCUNNWZJQ-UHFFFAOYSA-N 0.000 description 1
- MTCARZDHUIEYMB-UHFFFAOYSA-N 2-bromofluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Br)=CC=C3C2=C1 MTCARZDHUIEYMB-UHFFFAOYSA-N 0.000 description 1
- DMEVMYSQZPJFOK-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene Chemical group N1=NN=C2C3=CC=CC=C3C3=CC=NN=C3C2=N1 DMEVMYSQZPJFOK-UHFFFAOYSA-N 0.000 description 1
- YFCSASDLEBELEU-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene-11,12,15,16,17,18-hexacarbonitrile Chemical group N#CC1=C(C#N)C(C#N)=C2C3=C(C#N)C(C#N)=NN=C3C3=NN=NN=C3C2=C1C#N YFCSASDLEBELEU-UHFFFAOYSA-N 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 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 1
- IFFZVKXEHGJBIA-UHFFFAOYSA-N 9-naphthalen-1-yl-10-(4-naphthalen-2-ylphenyl)anthracene Chemical compound C12=CC=CC=C2C(C2=CC=C(C=C2)C2=CC3=CC=CC=C3C=C2)=C(C=CC=C2)C2=C1C1=CC=CC2=CC=CC=C12 IFFZVKXEHGJBIA-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- RDUBQTXEESZKOJ-UHFFFAOYSA-N CC(C)(C)C(C=C1C=C2C3=O)=CC=C1C2=CC=C3Br Chemical compound CC(C)(C)C(C=C1C=C2C3=O)=CC=C1C2=CC=C3Br RDUBQTXEESZKOJ-UHFFFAOYSA-N 0.000 description 1
- WXKUQOMEMWGSTI-UHFFFAOYSA-N CC(C)(C)C1=CC(=C(C=C1)C2=CC=C(C=C2)Cl)Br Chemical group CC(C)(C)C1=CC(=C(C=C1)C2=CC=C(C=C2)Cl)Br WXKUQOMEMWGSTI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical class C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000573 alkali metal alloy Inorganic materials 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000941 alkaline earth metal alloy Inorganic materials 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical class C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 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
- 238000011049 filling Methods 0.000 description 1
- 150000002219 fluoranthenes Chemical class 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical class C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000002964 pentacenes Chemical class 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a composite hole transport material and an organic electroluminescent element. A composite hole transport material includes a first compound having a structure represented by the following chemical formula A and a second compound having a structure represented by the following chemical formula B or C. The composite hole transport material provided by the invention is used as a hole transport layer material in an organic electroluminescent element, the service life of the composite hole transport material can be obviously prolonged, and meanwhile, the luminescent element has higher efficiency and stability and is more excellent in other service performance aspects.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent elements, in particular to a composite hole transport material and an organic electroluminescent element.
Background
Organic electroluminescent devices (OLEDs) are currently used in smart phones, tablet pcs, and vehicles due to their characteristics of lightness, thinness, wide viewing angle, high contrast, low power consumption, high response speed, full-color images, and flexibility, and are being expanded to large-sized applications such as televisions.
The organic electroluminescent device generally includes a plurality of film layers such as a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and the glass transition temperature of the film layers, the energy level matching between the film layers, the film formation quality and stability of the film layers, and the like all affect the performance of the device, and particularly, the driving voltage and the service life of the device are affected by the thermal stability of the hole transport material. To solve this problem, patent CN103515537B discloses a device using multiple hole transport layers, thereby solving the problem of reduced lifetime due to excessive charge injection; patents CN107004770B and CN110504375A disclose devices using a mixed hole transport layer, which is formed by mixing two materials, and the interface between the hole injection layer and the hole transport layer is reduced, thereby improving the efficiency and lifetime of the device. The use of the composite hole transport material provides further advantages in improving the lifetime of the device and maintaining device efficiency over the use of multiple hole transport layers.
However, the hole transport layer materials proposed at present are not ideal for improving the lifetime of organic electroluminescent devices, and there are very limited materials that can achieve the overall performance effects such as long lifetime and high efficiency.
Disclosure of Invention
The invention mainly aims to provide a composite hole transport material and an organic electroluminescent element, and aims to solve the problem that the hole transport layer material in the prior art is not ideal for improving the service life and the like of the organic electroluminescent element.
In order to achieve the above object, according to one aspect of the present invention, there is provided a composite hole transport material including a first compound having a structure represented by the following chemical formula a and a second compound having a structure represented by the following chemical formula B or C:
further, the composite hole transport material is prepared by the following method: mixing the first compound crude product and the second compound crude product to obtain a crude product mixture; carrying out sublimation purification on the crude product mixture to obtain a composite hole transport material; wherein the weight content of the first compound in the crude product mixture is 10-85%, and the weight content of the second compound in the crude product mixture is 10-85%.
Further, the weight content of the first compound in the crude product of the first compound is more than or equal to 98%, and the weight content of the second compound in the crude product of the second compound is more than or equal to 98%.
Further, the weight ratio of the first compound to the second compound is (1-3): 3-1.
Further, in the composite hole transport material, the weight ratio of the first compound to the second compound is 1 (2-3) or 2: 1.
Further, in the composite hole transport material, the purities of the first compound and the second compound are respectively more than 99.9%.
According to another aspect of the present invention, there is also provided an organic electroluminescent element comprising an anode, a cathode, and an organic material layer located between the anode and the cathode and comprising a hole transport layer, a light-emitting layer, and an electron transport layer, wherein the hole transport layer is formed of the above-described composite hole transport material.
Further, the organic electroluminescent element comprises an anode, a hole transport layer, a light emitting layer, an electron transport layer and a cathode which are sequentially stacked from bottom to top.
Further, the organic electroluminescent element further includes an efficiency improving layer, the efficiency improving layer being located between the hole transporting layer and the light emitting layer.
Further, the efficiency improvement layer comprises a hole injection layer, an electron blocking layer, a hole blocking layer and an electron injection layer which are sequentially stacked, the hole injection layer is arranged in contact with the hole transport layer, and the electron injection layer is arranged in contact with the light emitting layer.
The composite hole transport material provided by the invention is used as a hole transport layer material in an organic electroluminescent element, the service life of the composite hole transport material can be obviously prolonged, and meanwhile, the luminescent element has higher efficiency and stability and is excellent in other service performance aspects.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background of the invention section, the hole transport layer material in the prior art is not ideal for improving the lifetime of the organic electroluminescent device. In order to solve the above problems, the present invention provides a composite hole transport material, comprising a first compound having a structure represented by the following chemical formula a and a second compound having a structure represented by the following chemical formula B or C:
the composite hole transport material is used as a hole transport layer material in an organic electroluminescent element, the service life of the composite hole transport material can be obviously prolonged, and meanwhile, the luminescent element has high efficiency and stability and is excellent in other service performance aspects.
More preferably, the composite hole transport material is prepared by the following method: mixing the first compound crude product and the second compound crude product to obtain a crude product mixture; carrying out sublimation purification on the crude product mixture to obtain a composite hole transport material; wherein the weight content of the first compound in the crude product mixture is 10-85%, and the weight content of the second compound in the crude product mixture is 10-85%. Thus, the composite hole transport material is prepared by mixing the crude products of the two compounds in advance according to a certain proportion and then sublimating and purifying, so that the obtained composite material is more uniform in mixing, better in film forming property and convenient for mass production operation of the material. It should be noted that the proportions of the first compound and the second compound in the crude mixture are similar to those in the composite material finally sublimed, and may fluctuate slightly but not much, due to: the first compound and the second compound have the structures as described above, and the difference between the glass transition temperatures of the first compound and the second compound is small, and is within 10 ℃, even within 7 ℃, so that a relatively pure composite material can be obtained through the mixing and sublimation purification. This is because the glass transition temperature affects the sublimation temperature, and if the glass transition temperatures of the different components differ too much, sublimation together after mixing can damage materials with lower glass transition temperatures. The glass transition temperature difference between the selected compounds is small, so that the problem can be completely overcome.
More preferably, the weight content of the first compound in the crude product of the first compound is more than or equal to 98%, and the weight content of the second compound in the crude product of the second compound is more than or equal to 98%. Thus, on one hand, sublimation purification is more facilitated, and on the other hand, the purification pressure for preparing crude products at the early stage is also reduced.
In order to further improve the device lifetime, in a preferred embodiment, the weight ratio between the first compound and the second compound is (1-3): (3-1). Such as: the weight ratio between the first compound and the second compound is 1:1 or 2:1 or 3:1 or 1:2 or 1: 3. In the specific preparation process, the composite material with the ratio can be basically obtained only by controlling the ratio of the first compound to the second compound in the crude product mixture to be the same as the ratio in the sublimed composite material, for the reasons mentioned above, and the details are not repeated here. More preferably, the weight ratio of the first compound to the second compound is 1 (2-3) or 2: 1. Under the proportion, the service life of the device can be effectively prolonged, and other performances of the device, such as efficiency, can be further improved.
In a preferred embodiment, the first compound and the second compound each have a purity of greater than 99.9%.
According to another aspect of the present invention, there is also provided an organic electroluminescent element comprising an anode, a cathode, and an organic material layer located between the anode and the cathode and comprising a hole transport layer, a light-emitting layer, and an electron transport layer, wherein the hole transport layer is formed of the above-described composite hole transport material. The composite hole transport material is used as a hole transport layer material of the organic electroluminescent element, so that the service life of the device is effectively prolonged, and the device has other excellent properties.
In a preferred embodiment, the organic electroluminescent element includes, from bottom to top, an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode, which are stacked in this order. More preferably, the organic electroluminescent element further comprises an efficiency improving layer, the efficiency improving layer being located between the hole transporting layer and the light emitting layer. Preferably, the efficiency improvement layer includes a hole injection layer, an electron blocking layer, a hole blocking layer, and an electron injection layer, which are sequentially stacked, and the hole injection layer is disposed in contact with the hole transport layer and the electron injection layer is disposed in contact with the light emitting layer.
The cathode of the organic electroluminescent element is preferably selected from metals having a low work function (alkaline earth metals, alkali metals, main group metals, or lanthanoid), metal alloys (alloys of alkali metals or alkaline earth metals and silver), and may have a single-layer structure or a multi-layer structure. In the case of a multilayer structure, in addition to the metals having a low work function described above, other metals having a relatively high work function, such as Ag or Al, may also be used, usually combinations of metals, such as Ca/Ag, Mg/Ag or Ag/Ag. It may also be preferred to introduce a thin intermediate layer of a material having a high dielectric constant between the metal cathode and the organic semiconductor. The intermediate layer may be an alkali metal fluoride or an alkaline earth metal fluoride, or may be a corresponding oxide or carbonate (e.g., LiF, LiQ, BaF)2、MgO、NaF、 CsF、Cs2CO3Etc.).
The anode of the organic electroluminescent element preferably contains a metal material having a high work function, such as Ag, Pt, or Au. On the other hand, metal/metal oxide materials (e.g., Al/Ni/NiO, Al/PtO) may also be preferred2). Particularly preferred is Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO).
The hole injection layer of the organic electroluminescent element facilitates the reception of holes from the anode at low voltages, and preferably the Highest Occupied Molecular Orbital (HOMO) of the hole injection material should be secured between the work function of the anode material and the HOMO of the surrounding organic material layer, including but not limited to metalloporphyrins, oligothiophenes, anthraquinones, arylamine-based, hexacyano-Hexaazatriphenylene (HATCN), quinacridone-and perylene-based organic materials, polyaniline-based and polythiophene-based conductive polymers, and the like.
It should be noted that the hole transport layer of the organic electroluminescent device may be one or more layers, and as long as the material of one layer is the above-mentioned composite hole transport layer material, the device lifetime can be improved. The other hole transport layer is preferably the above-mentioned composite hole transport layer material, but may be other materials having higher hole mobility, such as organic materials including arylamine-based materials, conductive polymers, block copolymers having both conjugated and non-conjugated units, and the like, but is not limited thereto. The hole transport layer may receive holes from the anode or the hole injection layer and transport them to the light emitting layer.
The electron blocking layer of the organic electroluminescent element may block further transport of electrons in the light emitting layer to the anode to improve light emitting efficiency, and the electron blocking material needs to have a suitably high LUMO energy level, including, but not limited to, amine derivatives, fused aromatic amine derivatives, hexaazatriphenylene derivatives, fluorenylamine derivatives, spirobifluorenylamine derivatives, benzindenofluorenylamine derivatives, and the like.
The light-emitting layer of the organic electroluminescent element can receive holes and electrons from the hole transport layer and the electron transport layer, respectively, and cause the holes and electrons to combine with radiation to emit light. The host material of the light-emitting layer includes, but is not limited to, a fused aromatic ring derivative such as an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, and a fluoranthene compound, and a heteroaromatic ring derivative such as a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound, and a pyrimidine derivative.
The guest dopant material of the light-emitting layer of the organic electroluminescent element includes, but is not limited to, aromatic amine derivatives, styrene amine compounds, fluoranthene compounds, metal complexes, and the like.
The electron transport layer of the organic electroluminescent device can receive electrons from the cathode and transport the electrons to the light emitting layer, and the electron transport material needs to have high electron mobility, including derivatives such as oxazole, oxadiazole, triazole, imidazole, fluorenone, anthrone, metal complexes, nitrogen-containing five-membered ring derivatives, and the like, but is not limited thereto.
Further, the present invention provides an organic electroluminescent element comprising one or a combination of blue, green, red or yellow organic luminescent material layers; and the transverse direction or the longitudinal direction of the different organic light-emitting material layers are superposed and combined.
In a typical embodiment, the organic material layer is a plurality of layers, at least one of which is a hole transport layer and at least one of which is a hole injection layer, and both the hole transport layer and the hole injection layer contain the above-described organic compound.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Preparation of composite hole transport material
1. Synthesis of Compound A
1.1 Synthesis of intermediate A2
Fully drying the experimental device, adding 122g of 2-bromo-4 '-chloro-1, 1' -biphenyl (456mmo 1) and 1100mL of dried tetrahydrofuran into a 2L four-neck flask under nitrogen, stirring to dissolve, cooling to below-78 ℃ by using liquid nitrogen, and slowly dropwise adding 182.5mL of 2.5M (456mmol) n-BuLi n-hexane solution; stirring for 1h at-78 ℃ after the dropwise addition is finished, then adding 118g (455mmo1) of 2-bromo-9-fluorenone solid in batches at the temperature, preserving the temperature for 1h at-78 ℃ after the dropwise addition is finished, naturally heating to room temperature, and stirring for 12 h. After the reaction is finished, 4M hydrochloric acid solution is dripped to quench the reaction, ethyl acetate is used for extraction, the organic phase is washed by saturated brine, and the solvent is removed by spin drying, so that the intermediate alcohol A1 is obtained. Without any purification, a 2L dry three-necked flask was charged with 500mL of acetic acid and 15g of 36% hydrochloric acid, and the reaction was terminated by heating and refluxing for 3 hours. After cooling to room temperature, filtration, washing twice with water, drying and recrystallization from toluene and ethanol gave 121.6g of product A2 as an off-white solid in 58% yield.
1.2 Synthesis of intermediate A3
The experimental setup was dried thoroughly, 19.3g (45mmol) of 2-chloro-2 ' -bromo-9, 9' -spirobifluorene (A2) and 8.4g (49.5mmol) of diphenylamine were added to a 500mL four-necked flask under nitrogen, dried and degassed toluene was added as solvent, 6.5g (67.5mmol) of sodium tert-butoxide and 1.2g (2.25mmol) of the catalyst 1,1' -bis (diphenylphosphino) ferrocene (dppf) were added, the temperature was raised to 100 ℃ and 105 ℃ for 16 h. After the reaction was complete, it was cooled to room temperature, diluted with toluene, filtered over silica gel, and the filtrate was evaporated in vacuo to give a crude product which was dissolved in xylene for decolorization and recrystallized to give 22.4g of product A3 in 81% yield.
1.3 Synthesis of Compound A
The experimental set-up was thoroughly dried and to a 500mL four-necked flask, A3(20.7g, 40mmol) and N- [1,1' -biphenyl-2-yl were added under nitrogen]16.2g (45mmol) of-9, 9-dimethyl-9H-fluoren-2-amine, dried and degassed toluene as solvent, 6.1g (63mmol) of sodium tert-butoxide, 0.88g (0.96mmol) of Pd as catalyst2(dba)3Heating to 80 ℃, slowly dripping 4.5mL of tri-tert-butylphosphine toluene solution with the mass concentration of 10%, heating to 100-105 ℃ after dripping, and reacting for 6 h. After the reaction is finished, cooling to room temperature, diluting with toluene, filtering with silica gel pad, evaporating the solvent in the filtrate in vacuum to obtain a crude product, dissolving the crude product with xylene, decoloring and recrystallizing to obtain 26.6g of a compound A, wherein the yield is 72%, the HPLC purity is 98.6%, and MS [ M + H ]]+＝842.25。
2. Synthesis of Compound B
2.1 Synthesis of intermediate B1
In a 250mL three-necked flask, 9.4g (35mmol) of 2-bromo-4 '-chloro-1, 1' -biphenyl and 120mL of anhydrous tetrahydrofuran (dried) were added, cooled to-78 ℃ under nitrogen, 15.4mL (38.5mmol) of a 2.5M n-butyllithium n-hexane solution was slowly added, and stirred at-78 ℃ for 1.5 h; under the protection of nitrogen, 11g (35mmol) of 2-bromo-7-tert-butyl fluorenone is added in portions, the mixture is stirred to room temperature, and then the reaction is continued to be stirred for 2 hours. After the reaction is finished, adding a 4M hydrochloric acid solution to quench the reaction, extracting with ethyl acetate, washing an organic phase with saturated saline solution, removing the solvent by screwing, feeding the obtained oily liquid into a dry three-neck flask under the condition of no further purification, adding 150g of acetic acid and 3g of concentrated hydrochloric acid, heating and refluxing for 3 hours, and precipitating a large amount of solid. After the reaction was completed, it was cooled to room temperature, filtered, washed with water, dried, and recrystallized from toluene and ethanol to obtain 13.3g of off-white solid A1 with a yield of 65%.
The experimental set-up was dried thoroughly and 43.8g (90mmol) of intermediate B1 and 15.7g (93mmol) of diphenylamine were added to a 500mL four-necked flask under nitrogen, dried and degassed toluene was added as solvent, 11.3g (117.2mmol) of sodium tert-butoxide, 0.98g (0.9mmol) of Pd were added2(dba)3And 3.7g (1.85mmol) of a 10% tri-tert-butylphosphine toluene solution, and the reaction was carried out at 105 ℃ for 16 hours while heating to 100 ℃. After the reaction was complete, it was cooled to room temperature, diluted with toluene, filtered over silica gel, and the filtrate was vacuum distilled of the solvent to give a crude product which was dissolved in xylene for decolorization and recrystallized to give 44.1g of intermediate B2 as a white solid powder in 74% yield.
Into a 500mL dry four-necked flask were charged 18.4g (32mmol) of intermediate B2 and 12.3g (34mmol) of N- [1,1' -biphenyl-2-yl]-9, 9-dimethylbase-9H-fluoren-2-amine, then dried and degassed xylene as solvent, 4.8g (50mmol) sodium tert-butoxide, 0.32g (0.35mmol) Pd2(dba)3And 1.2g (0.6mmol) of 10% tri-tert-butylphosphine toluene solution, heating to 110 ℃ and 115 ℃ and reacting for 16 h. After the reaction is finished, cooling to room temperature, diluting with xylene, passing through a short column filled with silica gel, evaporating the solvent from the filtrate in vacuum to obtain a crude product, recrystallizing the crude product with toluene to obtain 21.2g of compound B as a white solid powder with a yield of 69%, an HPLC purity of 98.9%, and MS [ M + H ]]+＝898.54。
3. Synthesis of Compound C
3.1 Synthesis of intermediate C1
In a 250mL three-necked flask were added 11.3g (35mmol) of 2-bromo-4-tert-butyl 4 '-chloro-1, 1' -biphenyl and 120mL of anhydrous tetrahydrofuran (dried), cooled to-78 ℃ under nitrogen, 15.4mL (38.5mmol) of n-butyllithium was added slowly, and stirred at-78 ℃ for 1.5 h; 9.1g (35mmol) of 2-bromofluorenone is added in portions under the protection of nitrogen, the organic phase is washed by saturated saline solution, and the solvent is removed by rotation to obtain intermediate alcohol. Without further purification, the reaction mixture was charged into a dry three-necked flask, and 150g of acetic acid and 3g of concentrated hydrochloric acid were added thereto, and the mixture was refluxed for 3 hours at elevated temperature to complete the reaction. Cooling to room temperature, filtration and washing with water, drying and recrystallization from toluene and ethanol gave 14.7g of off-white solid C1 in 72% yield.
3.2 Synthesis of Compound C
The experimental set-up was thoroughly dried and to a 1000mL four-necked flask, under nitrogen, were added intermediate C150 g (102.9 mmol) and 17.4g (102.8mmol) diphenylamine, followed by dried and degassed toluene as solvent and 12.8g (133.7 mmol) sodium tert-butoxide, 0.5g (0.5mmol) Pd2(dba)3And 0.6g (1.1mmol) of 1,1' -bis (diphenylphosphine)) Ferrocene (dppf) was heated to slightly reflux (105-110 ℃ C.) and reacted for 4 hours. After the reaction is finished, cooling to 60 ℃, adding water for extraction washing, layering, enabling an upper layer organic phase to pass through a silica gel short column, evaporating the solvent in vacuum from the filtrate to obtain a crude product, and recrystallizing the crude product by using a toluene-n-hexane mixed solvent to obtain 45.8g of an intermediate C2, wherein the yield is 68%.
Into a 500mL dry four-necked flask, 21.8g (38mmol) of intermediate B2 and 14.4g (40 mmol) of N- [1,1' -biphenyl-2-yl were charged under nitrogen]-9, 9-dimethyl-9H-fluoren-2-amine, then dried and degassed xylene as solvent, 5.5g (57mmol) sodium tert-butoxide, 0.35g (0.38mmol) Pd2(dba)3And 1.6g (0.8mmol) of 10% tri-tert-butylphosphine toluene solution, heating to 110 ℃ and 115 ℃ and reacting for 16 h. After the reaction is finished, cooling to room temperature, diluting with xylene, filling silica gel into a short column, evaporating the solvent in the filtrate in vacuum to obtain a crude product, recrystallizing the crude product with toluene to obtain 26.8g of a compound C as white solid powder with HPLC purity of 98.7 percent and MS [ M + H ]]+＝898.56。
4. Preparation of composite materials
Respectively mixing the crude products of the compound A and the compound B according to the mass ratio of 1:3, 1:2, 1:1, 2:1 and 3:1, then carrying out vacuum sublimation purification, and finally respectively obtaining corresponding AB type composite materials 1A3B, 1A2B, 1A1B, 2A1B and 3A 1B. AC type composite materials 1A3C, 1A2C, 1A1C, 2A1C and 3A1C were prepared in the same manner, and the purity of the composite materials obtained by sublimation was 99.95% of compound a, compound B, compound C and the glass transition temperature (Tg) of each composite material as shown in table 1 below.
TABLE 1
| Name of Material | Tg(℃) |
| A | 142.92 |
| B | 145.20 |
| C | 149.76 |
| 1A3B | 144.47 |
| 1A2B | 143.83 |
| 1A1B | 143.61 |
| 2A1B | 143.46 |
| 3A1B | 143.24 |
| 1A3C | 147.59 |
| 1A2C | 146.93 |
| 1A1C | 145.54 |
| 2A1C | 144.25 |
| 3A1C | 144.27 |
Preparation of organic electroluminescent element
The composite material is particularly suitable for a hole transport layer in an organic electroluminescent element. The following examples and comparative examples illustrate in detail the effect of the organic compounds of the present invention as hole transport layers in organic electroluminescent devices, with reference to device structures.
The structural formula of the organic material used is as follows:
the organic electroluminescent element adopting the composite hole transport material can comprise a glass and transparent conducting layer (ITO) substrate layer 1, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5 and a cathode layer 6.
Device example 1
The method for manufacturing the OLED device by utilizing the Sunic sp1710 evaporator comprises the following specific steps: ultrasonically washing a glass substrate (Corning glass 40mm x 0.7mm) coated with ITO (indium tin oxide) with the thickness of 135nm for 5 minutes by using isopropanol and pure water respectively, cleaning by using ultraviolet ozone, and then conveying the glass substrate into a vacuum deposition chamber; a hole transport material HT1(N, N-bis ([1,1' -biphenylyl ] carbonitrile)) doped with 4% HD (4,4',4 "- ((1E,1' E, 1" E) -cyclopropane-1, 2, 3-triylidene tris (cyanomethylidene) tris (2,3,5, 6-tetrafluorobenzonitrile))]-4-yl) -9,9' -spirobifluoren-2-amine) at a thickness of 20nm in vacuum (about 10nm)-7Torr) is thermally deposited on the transparent ITO electrode to form a hole injection layer; a composite material 1A3B (compound a and compound B at a mass ratio of 1:3) was subsequently vacuum-deposited on the hole injection layer to a thickness of 60nm as a hole transport layer; vacuum deposition of 25nm doped 4% BD (N1, N6-bis (dibenzo [ b, d ]) on a hole transport layer]furan-4-yl) -N1, N6-bis (4-isopropylphenyl) 3, 8-diisopropylpyrene-1, 6-amine BH (9- (1-naphthyl) -10- (4- (2-naphthyl) phenyl) anthracene) as a light-emitting layer; then vacuum deposition of 50% LiQ (8-hydroxyquinoline lithium) doped ET (2- (9,9' -spirobi [ fluorene))]-2-yl) phenyl) -6- ([1,1' -biphenylyl]-3-yl) -2- (pyridin-3-yl) pyrimidine) Forming an electron transport layer with a thickness of 30 nm; finally depositing metal ytterbium (Yb, an electron injection layer) with the thickness of 2nm and magnesium-silver alloy with the doping ratio of 10:1 in sequence to form a cathode; finally the device was transferred from the deposition chamber to a glove box and then encapsulated with a UV curable epoxy and a glass cover plate containing a moisture absorbing agent.
In the above manufacturing steps, the deposition rates of the organic material, ytterbium metal and Mg metal were maintained at 0.1nm/s, 0.05 nm/s and 0.2nm/s, respectively.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20nm)/1A3B (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Device example 2
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, composite material 1A2B was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20nm)/1A2B (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Device example 3
An experiment was performed in the same manner as in example 1 except that: as the light-emitting layer, a composite material 1A1B was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20nm)/1A1B (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Device example 4
An experiment was performed in the same manner as in example 1 except that: as the light-emitting layer, composite material 2A1B was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20nm)/2A1B (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Device example 5
An experiment was performed in the same manner as in example 1 except that: as the light-emitting layer, a composite material 3A1B was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20nm)/3A1B (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Device example 6
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, composite material 1A3C was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20nm)/1A3C (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Device example 7
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, composite material 1A2C was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20nm)/1A2C (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Device example 8
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, composite material 1A1C was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20nm)/1A1C (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Device example 9
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, composite material 2A1C was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20nm)/2A1C (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Device example 10
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, composite material 3A1C was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20nm)/3A1C (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Comparative device example 1
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, compound a was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20 nm)/Compound A (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Comparative device example 2
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, compound B was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20 nm)/Compound B (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
Comparative device example 3
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, compound C was used instead of 1A3B in example 1.
The device structure is represented as: ITO (135nm)/HT1: 4% HD (20 nm)/Compound C (60nm)/HT2(10nm)/BH: 4% BD (25nm)/ET: LiQ (5:5,30nm) Yb (2nm)/Mg: Ag (10:1,150 nm).
The luminance, luminous efficiency, EQE (external quantum efficiency) of the device were measured by the french FS-100GA4 test in suzhou, and the device lifetime LT95 (initial luminance 4000nits, time taken to decay to 3800 nits) was measured in the french FS-MP96 test, all measurements being performed in a room temperature atmosphere. The device is at 10mA/cm2Specific performance data for operating voltage (V), current efficiency (C.E.), External Quantum Efficiency (EQE), and color coordinates (CIEx, CIEy) at current density are shown in table 2.
TABLE 2
As can be seen from the table, the above-described embodiments of the present invention achieve the following technical effects: device examples 1 to 10 prepared by using a composite material obtained by mixing the compound a with the compound B or the compound C as a hole transport layer have significantly improved device lifetimes compared to device comparative examples 1 to 3 in which a single material is used as a hole transport layer. In particular, in example 1, example 2, example 4, example 6, example 7, and example 9, the efficiency and lifetime of the device were simultaneously increased.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A composite hole transport material comprising a first compound having a structure represented by the following chemical formula A and a second compound having a structure represented by the following chemical formula B or C:
2. the composite hole transport material of claim 1, wherein the composite hole transport material is prepared by:
mixing the first compound crude product and the second compound crude product to obtain a crude product mixture; carrying out sublimation purification on the crude product mixture to obtain the composite hole transport material;
the weight content of the first compound in the crude product mixture is 10-85%, and the weight content of the second compound in the crude product mixture is 10-85%.
3. The composite hole transport material according to claim 2, wherein the weight content of the first compound in the crude first compound is not less than 98%, and the weight content of the second compound in the crude second compound is not less than 98%.
4. The composite hole transport material according to any one of claims 1 to 3, wherein the weight ratio between the first compound and the second compound is (1-3): (3-1).
5. The composite hole transport material according to claim 4, wherein the weight ratio of the first compound to the second compound in the composite hole transport material is 1 (2-3) or 2: 1.
6. The composite hole transport material according to any one of claims 1 to 5, wherein the first compound and the second compound each have a purity of more than 99.9%.
7. An organic electroluminescent element comprising an anode, a cathode, and an organic material layer which is located between the anode and the cathode and comprises a hole transport layer, a light-emitting layer, and an electron transport layer, characterized in that the hole transport layer is formed of the composite hole transport material according to any one of claims 1 to 6.
8. The organic electroluminescent element according to claim 7, wherein the organic electroluminescent element comprises, from bottom to top, the anode, the hole transport layer, the light-emitting layer, the electron transport layer, and the cathode, which are stacked in this order.
9. The organic electroluminescent element according to claim 8, further comprising an efficiency improvement layer between the hole transport layer and the light emitting layer.
10. The organic electroluminescent element according to claim 9, wherein the efficiency improvement layer comprises a hole injection layer, an electron blocking layer, a hole blocking layer, and an electron injection layer, which are sequentially stacked, and wherein the hole injection layer is disposed in contact with the hole transport layer and the electron injection layer is disposed in contact with the light-emitting layer.
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| CN103515537A (en) * | 2012-06-27 | 2014-01-15 | 三星显示有限公司 | Organic light-emitting device including multi-layered hole transport layer, and organic light-emitting display apparatus including the same |
| CN107004770A (en) * | 2014-10-24 | 2017-08-01 | 德山新勒克斯有限公司 | Utilize the display and organic electronic element of organic electronic element constituent |
| CN110066222A (en) * | 2018-10-25 | 2019-07-30 | 常州强力电子新材料股份有限公司 | Containing the fluorene structured organic compound of spiral shell two and its application in OLED device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103515537A (en) * | 2012-06-27 | 2014-01-15 | 三星显示有限公司 | Organic light-emitting device including multi-layered hole transport layer, and organic light-emitting display apparatus including the same |
| CN107004770A (en) * | 2014-10-24 | 2017-08-01 | 德山新勒克斯有限公司 | Utilize the display and organic electronic element of organic electronic element constituent |
| CN110066222A (en) * | 2018-10-25 | 2019-07-30 | 常州强力电子新材料股份有限公司 | Containing the fluorene structured organic compound of spiral shell two and its application in OLED device |
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