CN105576141A - Organic electroluminescence device - Google Patents
Organic electroluminescence device Download PDFInfo
- Publication number
- CN105576141A CN105576141A CN201610096055.6A CN201610096055A CN105576141A CN 105576141 A CN105576141 A CN 105576141A CN 201610096055 A CN201610096055 A CN 201610096055A CN 105576141 A CN105576141 A CN 105576141A
- Authority
- CN
- China
- Prior art keywords
- layer
- tin oxide
- indium
- anode
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 42
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical class [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 49
- 239000011737 fluorine Substances 0.000 claims abstract description 48
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011521 glass Substances 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 229910052738 indium Inorganic materials 0.000 claims abstract description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 134
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 239000010408 film Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 28
- 238000002347 injection Methods 0.000 claims description 27
- 239000007924 injection Substances 0.000 claims description 27
- 238000012986 modification Methods 0.000 claims description 27
- 230000004048 modification Effects 0.000 claims description 27
- 230000005540 biological transmission Effects 0.000 claims description 17
- 229910052741 iridium Inorganic materials 0.000 claims description 17
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 17
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 238000009832 plasma treatment Methods 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- -1 TiOPc (TiOPc) Chemical compound 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002346 layers by function Substances 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 4
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 3
- ZLZHPHUXJVYXTD-UHFFFAOYSA-N NCC=1C=C(C=CC1)C1=C(C=CC(=C1)N)C1=CC=C(C=C1)N Chemical class NCC=1C=C(C=CC1)C1=C(C=CC(=C1)N)C1=CC=C(C=C1)N ZLZHPHUXJVYXTD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- IWZZBBJTIUYDPZ-DVACKJPTSA-N (z)-4-hydroxypent-3-en-2-one;iridium;2-phenylpyridine Chemical compound [Ir].C\C(O)=C\C(C)=O.[C-]1=CC=CC=C1C1=CC=CC=N1.[C-]1=CC=CC=C1C1=CC=CC=N1 IWZZBBJTIUYDPZ-DVACKJPTSA-N 0.000 claims description 2
- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical compound C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 claims description 2
- LPCWDYWZIWDTCV-UHFFFAOYSA-N 1-phenylisoquinoline Chemical compound C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 LPCWDYWZIWDTCV-UHFFFAOYSA-N 0.000 claims description 2
- VDULMXJUOWIPGE-UHFFFAOYSA-N 1-phenylisoquinoline quinoline Chemical compound N1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)C1=NC=CC2=CC=CC=C12 VDULMXJUOWIPGE-UHFFFAOYSA-N 0.000 claims description 2
- ZEOMRHKTIYBETG-UHFFFAOYSA-N 2-phenyl-1,3,4-oxadiazole Chemical compound O1C=NN=C1C1=CC=CC=C1 ZEOMRHKTIYBETG-UHFFFAOYSA-N 0.000 claims description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 2
- HXWWMGJBPGRWRS-CMDGGOBGSA-N 4- -2-tert-butyl-6- -4h-pyran Chemical compound O1C(C(C)(C)C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(C(CCN2CCC3(C)C)(C)C)=C2C3=C1 HXWWMGJBPGRWRS-CMDGGOBGSA-N 0.000 claims description 2
- MWMNLUGPPZOPJQ-UHFFFAOYSA-N 4-(4-aminophenyl)-3-naphthalen-1-ylaniline Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1C1=CC=CC2=CC=CC=C12 MWMNLUGPPZOPJQ-UHFFFAOYSA-N 0.000 claims description 2
- WPUSEOSICYGUEW-UHFFFAOYSA-N 4-[4-(4-methoxy-n-(4-methoxyphenyl)anilino)phenyl]-n,n-bis(4-methoxyphenyl)aniline Chemical compound C1=CC(OC)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 WPUSEOSICYGUEW-UHFFFAOYSA-N 0.000 claims description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 claims description 2
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- BCIKXVCYWZORHA-UHFFFAOYSA-N 5,6,11,12-tetraphenylchrysene Chemical compound C1(=CC=CC=C1)C1=C(C2=CC=CC=C2C=2C(=C(C=3C=CC=CC=3C=21)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 BCIKXVCYWZORHA-UHFFFAOYSA-N 0.000 claims description 2
- UOOBIWAELCOCHK-BQYQJAHWSA-N 870075-87-9 Chemical compound O1C(C(C)C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(C(CCN2CCC3(C)C)(C)C)=C2C3=C1 UOOBIWAELCOCHK-BQYQJAHWSA-N 0.000 claims description 2
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 claims description 2
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 claims description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 2
- CECAIMUJVYQLKA-UHFFFAOYSA-N iridium 1-phenylisoquinoline Chemical compound [Ir].C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 CECAIMUJVYQLKA-UHFFFAOYSA-N 0.000 claims description 2
- RTRAMYYYHJZWQK-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1 RTRAMYYYHJZWQK-UHFFFAOYSA-N 0.000 claims description 2
- YRZZLAGRKZIJJI-UHFFFAOYSA-N oxyvanadium phthalocyanine Chemical compound [V+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 YRZZLAGRKZIJJI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- VLRICFVOGGIMKK-UHFFFAOYSA-N pyrazol-1-yloxyboronic acid Chemical compound OB(O)ON1C=CC=N1 VLRICFVOGGIMKK-UHFFFAOYSA-N 0.000 claims description 2
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 3
- 238000005036 potential barrier Methods 0.000 description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- XZJBGQPXSSPRBY-UHFFFAOYSA-N [C].B(F)(F)F Chemical compound [C].B(F)(F)F XZJBGQPXSSPRBY-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PMWGIVRHUIAIII-UHFFFAOYSA-N 2,2-difluoropropanoic acid Chemical compound CC(F)(F)C(O)=O PMWGIVRHUIAIII-UHFFFAOYSA-N 0.000 description 1
- 229910019015 Mg-Ag Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- 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
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
-
- 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
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/816—Multilayers, e.g. transparent multilayers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The embodiment of the invention discloses an organic electroluminescence device which comprises an anode, a function layer, a luminescence layer and a cathode, wherein the anode is a modified indium tin oxide anode which comprises an indium tin oxide anode and a modifying layer; the indium tin oxide anode comprises a glass substrate and an indium tin oxide film arranged on the surface of the glass substrate; the modifying layer is arranged on the surface of the indium tin oxide film and is a fluorine-containing dipole layer formed by the bonding of indium on the surface of the indium tin oxide film and fluorine and existing in a form of In-F; the mass percentage content of the fluorine element in the fluorine-containing dipole layer is 11-20%; and the mass percentage content ratio of the tin element to indium element is 0.004-0.017. With the fluorine-containing dipole layer, the work content of the anode surface is improved.
Description
Technical field
The present invention relates to electronic device association area, particularly relate to a kind of organic electroluminescence device.
Background technology
At present, in organic semiconductor industry, organic electroluminescence device (OLED) has the characteristics such as brightness is high, material selection range is wide, driving voltage is low, all solidstate active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, be a kind of Display Technique and light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, be the focal point of current lot of domestic and foreign researcher.
In the structure of organic electroluminescence device, anode, as a pith of device architecture, carries the effect that carrier injection is connected with circuit, and the injection of charge carrier is relevant with the interface potential barrier between organic material with electrode simultaneously.Anode is all generally bear the effect of injecting in hole, the conductive oxide film of usual employing is as tin indium oxide (ITO) etc., its work content only has 4.7eV, and the organic hole transport material adopted, its HOMO energy level is usually at about 5.1V, cause hole to inject needs like this and overcome larger potential barrier, thus cause hole injection efficiency not high.Improve the work content of ITO, will greatly be conducive to the injection efficiency improving hole.The general object being realized raising work content by the Sn/In ratio of reduction ITO surface-element or the content of raising surface oxygen atoms, in addition, is formed dipole layer at anode surface and also can reach this effect at present.
Summary of the invention
For solving the problems of the technologies described above, the present invention aims to provide a kind of modification indium-tin oxide anode and preparation method thereof, the method is by carrying out moditied processing by indium-tin oxide anode surface, indium tin oxide films surface is made to define fluorine-containing dipole layer, improve anode surface work content, thus make this anode greatly can improve the injection efficiency in hole in the application, improve device light emitting efficiency.Present invention also offers the organic electroluminescence device comprising above-mentioned modification indium-tin oxide anode.
First aspect, the invention provides a kind of modification indium-tin oxide anode, comprise indium-tin oxide anode and decorative layer, described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface, described decorative layer is arranged on described indium tin oxide films surface, described decorative layer is the indium on described indium tin oxide films surface becomes key the to be formed fluorine-containing dipole layer existed with In-F form with fluorine, the mass percentage of the fluorine element of described fluorine-containing dipole layer is 11 ~ 20%, and tin element is 0.004 ~ 0.017 with the mass percentage ratio of phosphide element.
Preferably, the thickness of described indium tin oxide films is 70 ~ 200nm.
Second aspect, the invention provides a kind of preparation method modifying indium-tin oxide anode, comprises the following steps:
Described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface;
It is in the fluorine-containing aqueous solutions of organic acids of 0.2 ~ 2mol/L that described indium-tin oxide anode is immersed concentration, soaks after 0.5 ~ 2 minute, take out at 5 ~ 20 DEG C, dry;
Dried described indium-tin oxide anode is placed in plasma apparatus, pass into fluoro-gas, the gas pressure in plasma apparatus is made to be 10Pa ~ 60Pa, adjustment radio-frequency power is 40w ~ 100w, carry out plasma treatment 5 ~ 10 minutes, obtain modifying indium-tin oxide anode, the surface of described modification indium-tin oxide anode has decorative layer, and described decorative layer is the indium on described indium tin oxide films surface becomes key the to be formed fluorine-containing dipole layer existed with In-F form with fluorine.
The percentage composition of the fluorine element of described fluorine-containing dipole layer is 11 ~ 20%, and tin element is 0.004 ~ 0.017 with the mass percentage ratio of phosphide element.
Described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface.Prepare in the following way: clean glass substrate is provided, adopt magnetron sputtering method Slag coating indium tin oxide films on described glass substrate.
Described glass substrate is commercially available simple glass.
Preferably, the cleaning operation of described glass substrate is specially: adopt liquid detergent, deionized water, isopropyl alcohol and acetone to carry out ultrasonic cleaning 20 minutes respectively successively, then nitrogen dries up.
Preferably, the thickness of described indium tin oxide films is 70 ~ 200nm.
It is in the fluorine-containing aqueous solutions of organic acids of 0.2 ~ 2mol/L that described indium-tin oxide anode is immersed concentration, soaks after 0.5 ~ 2 minute, take out at 5 ~ 20 DEG C, dry.
Preferably, described fluorine-containing organic acid is difluoroacetic acid, trifluoroacetic acid or 2,2-difluoro propionic acid.
Preferably, the concentration of described fluorine-containing aqueous solutions of organic acids is 0.5 ~ 1mol/L.
The concrete mode of described drying does not do particular restriction.Preferably, described drying process was: 50 ~ 80 DEG C of vacuumizes 12 ~ 24 hours.
Described indium-tin oxide anode is by after fluorine-containing organic acid preliminary treatment, its adsorption has a large amount of functional fluoropolymer group, because fluorine has strong electron-withdrawing power, therefore these functional fluoropolymer groups will at tin indium oxide (ITO) surface and indium In forming section In-F key, thus the part Sn on tin indium oxide (ITO) surface is replaced by F, but the In-F key now formed is not very stable, need do further process.
Dried described indium-tin oxide anode is placed in plasma apparatus, passes into fluoro-gas and carry out plasma treatment, obtain modifying indium-tin oxide anode.The surface of this modification indium-tin oxide anode has decorative layer, and described decorative layer is the fluorine-containing dipole layer existed with In-F form that In and the F on described indium tin oxide films surface becomes key to be formed.
Preferably, described fluoro-gas is carbon tetrafluoride or borontrifluoride carbon.
In plasma treatment procedure, the gas pressure in plasma apparatus is 10 ~ 60Pa, and radio-frequency power is 40 ~ 100w, and the time of plasma treatment is 5 ~ 10 minutes.
Indium-tin oxide anode, after fluoro-gas plasma treatment, becomes more stable by making unstable In-F key; Meanwhile, the fluorine in fluoro-gas also can form In-F key with the indium on ITO surface (In), and the tin (Sn) on ITO surface is replaced by fluorine (F) further; In addition, the functional fluoropolymer group of key that do not become with ITO being adsorbed on surface after fluorine-containing organic acid preliminary treatment also will form In-F key with In, thus further increase the In-F key ratio on ITO surface, improve the percentage composition of anode surface element F, decrease the Sn/In constituent content ratio of anode surface.So, at the fluorine-containing dipole layer that anode ITO surface will define one deck and exists with In-F form, the percentage composition of the fluorine element of this fluorine-containing dipole layer is 11 ~ 20%, tin element is 0.004 ~ 0.017 with the mass percentage ratio of phosphide element, therefore, relative to the ito anode of common unmodified, this fluorine-containing dipole layer exists as decorative layer can improve ito anode surface work content, thus the potential barrier needing to overcome is injected in reduction hole, improves hole injection efficiency.This is because the existence of dipole layer will improve the vacuum level E on ITO surface
vac, improve a numerical value δ, make Fermi level EF and the vacuum level E of anode like this
vacdifference DELTA E compare the many δ of original difference.According to the definition of work content, work content is the difference of material Fermi level and vacuum level, so just means that work content improves δ numerical value.Namely the existence of fluorine-containing dipole layer improves anode surface work content.
Described modification indium-tin oxide anode should properly be preserved, and Conservation environment is vacuum environment < 10
-3pa or be kept at N
2in glove box.
The third aspect, the invention provides a kind of organic electroluminescence device, comprise anode, functional layer, luminescent layer and negative electrode, described anode is for modifying indium-tin oxide anode, described modification indium-tin oxide anode comprises indium-tin oxide anode and decorative layer, described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface, described decorative layer is arranged on described indium tin oxide films surface, described decorative layer is the indium on described indium tin oxide films surface becomes key the to be formed fluorine-containing dipole layer existed with In-F form with fluorine, the mass percentage of the fluorine element of described fluorine-containing dipole layer is 11 ~ 20%, tin element is 0.004 ~ 0.017 with the mass percentage ratio of phosphide element.
Preferably, the thickness of described indium tin oxide films is 70 ~ 200nm.
Wherein, described functional layer comprises at least one in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer.
When described functional layer is multilayer, described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are successively set on the ito thin film surface modifying indium-tin oxide anode in order.
The material of described hole injection layer can be Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc) or 4,4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA).The thickness of hole injection layer is 10 ~ 40nm.
The hole mobile material of described hole transmission layer can be N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD); N, N, N ', N '-tetramethoxy phenyl)-benzidine (MeO-TPD); 2, two (the N of 7-, N-bis-(4-methoxyphenyl) is amino)-9,9-spiral shell two fluorenes (MeO-Sprio-TPD), N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 1,1-bis-(4-(N, N '-two (p-tolyl) is amino) phenyl) cyclohexane (TAPC) or 2,2 ', 7,7 '-four (N, N-hexichol amido)-9,9 '-spiral shell two fluorenes (S-TAD), the thickness of hole transmission layer is 20 ~ 50nm.
The material of described luminescent layer is the composite material that luminescent material doping hole mobile material or electron transport material are formed.
Described luminescent material can be 4-(dintrile methyl)-2-T base-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 2, 3, 6, 7-tetrahydrochysene-1, 1, 7, 7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9, 9A, 1GH] cumarin (C545T), two (2-methyl-oxine)-(4-xenol) aluminium (BALQ), 4-(dintrile methene)-2-isopropyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq3), 5, 6, 11, 12-tetraphenyl naphthonaphthalene (Rubrene), 4, 4 '-two (2, 2-diphenylethyllene)-1, 1 '-biphenyl (DPVBi), two (4, 6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium (FIrpic), two (4, 6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid conjunction iridium (FIr6), two (4, 6-bis-fluoro-5-cyano-phenyl pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium (FIrN4), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq) 2 (acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2 (acac)), three (1-phenyl-isoquinolin) close one or more that iridium (Ir (piq) 3) or three (2-phenylpyridines) close in iridium (Ir (ppy) 3).The thickness of luminescent layer is 10 ~ 20nm.
The electron transport material of described electron transfer layer can be 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (as TAZ) or two (2-methyl-oxine-N
1, O
8)-(1,1 '-biphenyl-4-hydroxyl) aluminium (BAlq).The thickness of electron transfer layer is 30 ~ 60nm.
The material of described electron injecting layer can be LiF, CsF or NaF, and thickness is 1nm;
Described negative electrode can adopt Ag, Al, Sm, Yb, Mg-Ag alloy or Mg-Al alloy, and thickness is 70 ~ 200nm.
Above-mentioned hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode all can adopt the mode of vacuum evaporation to be prepared in successively and modify in indium-tin oxide anode.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) preparation method of modification indium-tin oxide anode provided by the invention, by indium-tin oxide anode is carried out fluorine-containing organic acid preliminary treatment and fluoro-gas plasma treatment, decrease the Sn/In constituent content ratio of anode surface, make indium-tin oxide anode surface define decorative layer simultaneously, namely with the fluorine-containing dipole layer that the form of In-F exists, thus improve anode surface work content;
(2) preparation method of modification indium-tin oxide anode provided by the invention, technique is simple, and cost is low;
(3) modification indium-tin oxide anode provided by the invention, can be widely used in organic electroluminescence device and organic solar batteries, improves the efficiency of device.
Accompanying drawing explanation
Fig. 1 is the structure chart of the organic electroluminescence device that the embodiment of the present invention 1 provides;
Fig. 2 is the organic electroluminescence device that provides of the embodiment of the present invention 4 and the current density of existing organic electroluminescence device and the graph of a relation of voltage.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
Modify a preparation method for indium-tin oxide anode, comprise the following steps:
(1) get glass substrate, adopt liquid detergent, deionized water, isopropyl alcohol and acetone to carry out ultrasonic cleaning 20 minutes respectively successively, then nitrogen dries up; Adopt magnetron sputtering method to prepare the indium tin oxide films that thickness is 100nm on the glass substrate, obtain indium-tin oxide anode;
(2) described indium-tin oxide anode being immersed concentration is in the difluoroacetic acid aqueous solution of 2mol/L, soaks after 0.5 minute, take out at 10 DEG C, 50 DEG C of vacuumize 12 hours;
(3) dried indium-tin oxide anode is placed in plasma apparatus, passes into carbon tetrafluoride (CF
4) gas carries out plasma treatment, obtains modifying indium-tin oxide anode, the surface modifying indium-tin oxide anode has decorative layer, decorative layer be In and the F on indium tin oxide films surface become key to be formed with the fluorine-containing dipole layer of In-F form existence.
In plasma treatment procedure, the gas pressure in plasma apparatus is 10Pa, and radio-frequency power is 50w, and the time of plasma treatment is 6 minutes.
The modification indium-tin oxide anode that the present embodiment is obtained, its finishing coat is the fluorine-containing dipole layer existed with the form of In-F, and this dipole layer will improve the vacuum level E on ITO surface
vac, improve a numerical value δ, make the Fermi level E of anode like this
fwith vacuum level E
vacdifference DELTA E compare the many δ of original difference.According to the definition of work content, work content is the difference of material Fermi level and vacuum level, so just means that work content improves δ numerical value.The surperficial work content of not modified indium-tin oxide anode is generally 4.7eV, and the surperficial work content of the modification indium-tin oxide anode that the present embodiment prepares is 5.7eV.
Embodiment 2
Modify a preparation method for indium-tin oxide anode, comprise the following steps:
(1) get glass substrate, adopt liquid detergent, deionized water, isopropyl alcohol and acetone to carry out ultrasonic cleaning 20 minutes respectively successively, then nitrogen dries up; Adopt magnetron sputtering method to prepare the indium tin oxide films that thickness is 70nm on the glass substrate, obtain indium-tin oxide anode;
(2) indium-tin oxide anode being immersed concentration is in the trifluoroacetic acid aqueous solution of 0.2mol/L, soaks after 2 minutes at 20 DEG C, takes out, 80 DEG C of vacuumize 12 hours;
(3) dried indium-tin oxide anode is placed in plasma apparatus, passes into borontrifluoride carbon (CHF
3) gas carries out plasma treatment, obtains modifying indium-tin oxide anode, the surface modifying indium-tin oxide anode has decorative layer, decorative layer be In and the F on indium tin oxide films surface become key to be formed with the fluorine-containing dipole layer of In-F form existence.
In plasma treatment procedure, the gas pressure in plasma apparatus is 30Pa, and radio-frequency power is 40w, and the time of plasma treatment is 10 minutes.
The surperficial work content of the modification indium-tin oxide anode that the present embodiment prepares is 5.8eV.
Embodiment 3
Modify a preparation method for indium-tin oxide anode, comprise the following steps:
(1) get glass substrate, adopt liquid detergent, deionized water, isopropyl alcohol and acetone to carry out ultrasonic cleaning 20 minutes respectively successively, then nitrogen dries up; Adopt magnetron sputtering method to prepare the indium tin oxide films that thickness is 200nm on the glass substrate, obtain indium-tin oxide anode;
(2) indium-tin oxide anode being immersed concentration is in 2, the 2-difluoro propionic acid aqueous solution of 1mol/L, soaks after 1 minute at 5 DEG C, takes out, 60 DEG C of vacuumize 24 hours;
(3) dried indium-tin oxide anode is placed in plasma apparatus, passes into carbon tetrafluoride (CF
4) gas carries out plasma treatment, obtains modifying indium-tin oxide anode, the surface modifying indium-tin oxide anode has decorative layer, decorative layer be In and the F on indium tin oxide films surface become key to be formed with the fluorine-containing dipole layer of In-F form existence.
In plasma treatment procedure, the gas pressure in plasma processing chamber is 60Pa, and radio-frequency power is 100w, and the time of plasma treatment is 5 minutes.
The surperficial work content of the modification indium-tin oxide anode that the present embodiment prepares is 5.9eV.
The above embodiment of the present invention 1 ~ 3 gained modification indium-tin oxide anode and not modified common indium-tin oxide anode are carried out surface-element analysis, method of testing adopts XPS (x-ray photoelectron spectroscopy), INSTRUMENT MODEL is ESCA2000 (VGMicrotechInc. company), test condition is for using Al target K alpha ray source, and ray energy is 1486.6eV.Calculate the 1s track of ito thin film surface C element respectively, the 3d of In element
5/2track, the 3d of Sn element
5/2the 1s track of track O element, the 1s track of F element, calculate each element percentage composition, its testing result is as shown in table 1.
Table 1
As can be seen from Table 1, not modified common indium-tin oxide anode, its surface is by C, O, In, Sn tetra-kinds of element compositions, modification indium-tin oxide anode after the inventive method moditied processing, surface how F element, illustrates through moditied processing, F element becomes key to be formed in ito thin film surface with In, thus defines on ito thin film surface the fluorine-containing dipole layer existed with In-F form.As can be seen from Elemental analysis data result, modification indium-tin oxide anode prepared by the present invention, the percentage composition of the F element of its fluorine-contained surface dipole layer reaches more than 11%, has been up to 19.46%.Simultaneously by moditied processing of the present invention, the Sn/In on ITO surface reduces than significantly, has minimumly dropped to 0.004 from 0.188.Illustrate that F instead of the key mapping of part Sn, become key with In.
Embodiment 4
A kind of organic electroluminescence device, comprises the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and described anode is modification indium-tin oxide anode prepared by the embodiment of the present invention 1.
Particularly, in the present embodiment, the material of hole injection layer is Phthalocyanine Zinc (ZnPc), and thickness is 15nm; The material of hole transmission layer is N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD), and thickness is 50nm; The material of luminescent layer is that three (2-phenylpyridines) close iridium (Ir (ppy)
3) 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) composite material that benzene (TPBi) is formed of 8% mass fraction that adulterates, be expressed as Ir (ppy)
3: TPBi (8%), thickness is 15nm; The electron transport material of electron transfer layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi), and thickness is 50nm; The material of electron injecting layer is LiF, and thickness is 1nm; Negative electrode is Ag, and thickness is 100nm.
The structure of the present embodiment organic electroluminescence device is: ito anode/decorative layer/ZnPc (15nm)/TPD (50nm)/Ir (ppy)
3: TPBi (8%, 15nm)/TPBi (50nm)/LiF (1nm)/Ag (100nm).
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, the structure of this organic electroluminescence device comprises, and modifies ito anode 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and negative electrode 70.Wherein, modify ito anode 10 and comprise ito anode 101 and decorative layer 102, described decorative layer 102 is there is fluorine-containing dipole layer with the form of In-F.
Compared with existing organic electroluminescence device, embodiment of the present invention organic electroluminescence device is owing to have employed modification indium-tin oxide anode, and anode surface work content improves, and hole injection efficiency improves, thus the starting resistor of device is obviously reduced.The structure of existing organic electroluminescence device is: common unmodified ito anode/ZnPc (15nm)/TPD (50nm)/Ir (ppy)
3: TPBi (8%, 15nm)/TPBi (50nm)/LiF (1nm)/Ag (100nm).The starting resistor of existing organic electroluminescence device is 3.0eV, and the starting resistor of the present embodiment organic electroluminescence device is 2.1eV.
Fig. 2 is the organic electroluminescence device of the present embodiment and the current density of existing luminescent device and the graph of a relation of voltage.Wherein, curve 1 is the current density of the present embodiment organic electroluminescence device and the graph of a relation of voltage; Curve 2 is the current density of existing organic electroluminescence device and the graph of a relation of voltage.As can be seen from the figure, under identical starting resistor, the present embodiment organic electroluminescence device can obtain higher Injection Current, thus makes device have higher luminous efficiency.The luminous efficiency of existing organic electroluminescence device is 13.1lm/W, and the luminous efficiency of the present embodiment organic electroluminescence device is 26.4lm/W.This is because the present embodiment organic electroluminescence device have employed modification indium-tin oxide anode, improves the injection efficiency in hole, therefore, it is possible to obtain higher Carrier Injection Efficiency, improves device organic electroluminescent efficiency.
Embodiment 5
A kind of organic electroluminescence device, comprises the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and described anode is modification indium-tin oxide anode prepared by the embodiment of the present invention 2.The material of described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode and embodiment 4 are together.
The starting resistor of the present embodiment organic electroluminescence device is 2.1eV, and luminous efficiency is 31.1lm/w.
Embodiment 6
A kind of organic electroluminescence device, comprises the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and described anode is modification indium-tin oxide anode prepared by the embodiment of the present invention 3.The material of described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode and embodiment 4 are together.
The starting resistor of the present embodiment organic electroluminescence device is 2.0eV, and luminous efficiency is 35.2lm/w.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, comprise anode, functional layer, luminescent layer and negative electrode, described anode is for modifying indium-tin oxide anode, described modification indium-tin oxide anode comprises indium-tin oxide anode and decorative layer, described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface, described decorative layer is arranged on described indium tin oxide films surface, described decorative layer is the indium on described indium tin oxide films surface becomes key the to be formed fluorine-containing dipole layer existed with In-F form with fluorine, the mass percentage of the fluorine element of described fluorine-containing dipole layer is 11 ~ 20%, tin element is 0.004 ~ 0.017 with the mass percentage ratio of phosphide element, described modification indium-tin oxide anode adopts following steps to be prepared from:
Clean indium-tin oxide anode is provided; Described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface;
It is in the fluorine-containing aqueous solutions of organic acids of 0.2 ~ 2mol/L that described indium-tin oxide anode is immersed concentration, soaks after 0.5 ~ 2 minute, take out at 5 ~ 20 DEG C, dry;
Dried described indium-tin oxide anode is placed in plasma apparatus, pass into fluoro-gas, the gas pressure in plasma apparatus is made to be 10Pa ~ 60Pa, adjustment radio-frequency power is 40w ~ 100w, carry out plasma treatment 5 ~ 10 minutes, obtain modifying indium-tin oxide anode, the surface of described modification indium-tin oxide anode has decorative layer, and described decorative layer is the indium on described indium tin oxide films surface becomes key the to be formed fluorine-containing dipole layer existed with In-F form with fluorine.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described indium tin oxide films is 70 ~ 200nm.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, described functional layer comprises at least one in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer.
4. organic electroluminescence device as claimed in claim 3, it is characterized in that, when described functional layer is multilayer, described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are successively set on the ito thin film surface modifying indium-tin oxide anode in order.
5. organic electroluminescence device as claimed in claim 3, it is characterized in that, the material of described hole injection layer can be Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc) or 4,4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA).The thickness of hole injection layer is 10 ~ 40nm.
6. organic electroluminescence device as claimed in claim 3, it is characterized in that, the hole mobile material of described hole transmission layer can be N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD); N, N, N ', N '-tetramethoxy phenyl)-benzidine (MeO-TPD); 2, two (the N of 7-, N-bis-(4-methoxyphenyl) is amino)-9,9-spiral shell two fluorenes (MeO-Sprio-TPD), N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 1,1-bis-(4-(N, N '-two (p-tolyl) is amino) phenyl) cyclohexane (TAPC) or 2,2 ', 7,7 '-four (N, N-hexichol amido)-9,9 '-spiral shell two fluorenes (S-TAD), the thickness of hole transmission layer is 20 ~ 50nm.
7. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described luminescent layer is the composite material that luminescent material doping hole mobile material or electron transport material are formed.
8. organic electroluminescence device as claimed in claim 7, it is characterized in that, described luminescent material can be 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 2, 3, 6, 7-tetrahydrochysene-1, 1, 7, 7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9, 9A, 1GH] cumarin (C545T), two (2-methyl-oxine)-(4-xenol) aluminium (BALQ), 4-(dintrile methene)-2-isopropyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq3), 5, 6, 11, 12-tetraphenyl naphthonaphthalene (Rubrene), 4, 4 '-two (2, 2-diphenylethyllene)-1, 1 '-biphenyl (DPVBi), two (4, 6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium (FIrpic), two (4, 6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid conjunction iridium (FIr6), two (4, 6-bis-fluoro-5-cyano-phenyl pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium (FIrN4), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq) 2 (acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2 (acac)), three (1-phenyl-isoquinolin) close one or more that iridium (Ir (piq) 3) or three (2-phenylpyridines) close in iridium (Ir (ppy) 3).The thickness of luminescent layer is 10 ~ 20nm.
9. organic electroluminescence device as claimed in claim 3, it is characterized in that, the electron transport material of described electron transfer layer can be 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1, 3, 4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 4, 7-diphenyl-o-phenanthroline (Bphen), 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP), 1, 2, 4-triazole derivative (as TAZ) or two (2-methyl-oxine-N
1, O
8)-(1,1 '-biphenyl-4-hydroxyl) aluminium (BAlq).The thickness of electron transfer layer is 30 ~ 60nm.
10. organic electroluminescence device as claimed in claim 3, it is characterized in that, above-mentioned hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode all can adopt the mode of vacuum evaporation to be prepared in successively and modify in indium-tin oxide anode.
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| CN106601924A (en) * | 2016-12-21 | 2017-04-26 | 浙江大学 | A quantum dot light-emitting diode and its preparation method |
| CN111384271A (en) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
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| CN107863451B (en) * | 2017-10-30 | 2019-06-25 | 武汉华星光电技术有限公司 | A kind of preparation method of OLED anode and the preparation method of OLED display |
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| CN103928628A (en) | 2014-07-16 |
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