CN105576141B - A kind of organic electroluminescence device - Google Patents
A kind of organic electroluminescence device Download PDFInfo
- Publication number
- CN105576141B CN105576141B CN201610096055.6A CN201610096055A CN105576141B CN 105576141 B CN105576141 B CN 105576141B CN 201610096055 A CN201610096055 A CN 201610096055A CN 105576141 B CN105576141 B CN 105576141B
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- China
- Prior art keywords
- indium
- layer
- tin oxide
- 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.)
- Expired - Fee Related
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- 238000005401 electroluminescence Methods 0.000 title claims abstract description 41
- 239000010410 layer Substances 0.000 claims abstract description 142
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 53
- 239000011737 fluorine Substances 0.000 claims abstract description 48
- 230000004048 modification Effects 0.000 claims abstract description 41
- 238000012986 modification Methods 0.000 claims abstract description 41
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 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 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 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
- 239000002346 layers by function Substances 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 33
- 238000002347 injection Methods 0.000 claims description 29
- 239000007924 injection Substances 0.000 claims description 29
- 239000010408 film Substances 0.000 claims description 25
- 229910052741 iridium Inorganic materials 0.000 claims description 19
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 230000005540 biological transmission Effects 0.000 claims description 16
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- -1 TiOPc (TiOPc) Chemical compound 0.000 claims description 9
- 238000003851 corona treatment Methods 0.000 claims description 9
- 238000006664 bond formation reaction Methods 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 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
- 230000005525 hole transport Effects 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-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
- 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
- LPCWDYWZIWDTCV-UHFFFAOYSA-N 1-phenylisoquinoline Chemical class C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 LPCWDYWZIWDTCV-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 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
- ZEOMRHKTIYBETG-UHFFFAOYSA-N 2-phenyl-1,3,4-oxadiazole Chemical class 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
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 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
- 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 class 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
- 239000005725 8-Hydroxyquinoline Substances 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
- 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
- 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 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
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229960003540 oxyquinoline Drugs 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-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
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims 1
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical class C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical compound [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims 1
- 239000007789 gas Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 9
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 6
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 4
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005036 potential barrier Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 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
- 239000001301 oxygen Substances 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
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910019015 Mg-Ag Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- IYWUYZIACVBVNP-UHFFFAOYSA-N N-[4-(4-aminophenyl)phenyl]-2,3,4,5-tetramethoxyaniline Chemical compound COC=1C(=C(C(=C(C=1)NC1=CC=C(C2=CC=C(N)C=C2)C=C1)OC)OC)OC IYWUYZIACVBVNP-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000009467 reduction Effects 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
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-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
-
- 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
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- 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
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Abstract
The embodiment of the invention discloses a kind of organic electroluminescence device, including anode, functional layer, luminescent layer and negative electrode, the anode is modification indium-tin oxide anode, the modification indium-tin oxide anode includes indium-tin oxide anode and decorative layer, the indium-tin oxide anode includes glass substrate and is arranged on the indium tin oxide films of the glass baseplate surface, the decorative layer is arranged on the indium tin oxide films surface, the fluorine-containing dipole layer existed in In F forms that the decorative layer is formed for the indium on the indium tin oxide films surface with fluorine bonding, the weight/mass percentage composition of the fluorine element of the fluorine-containing dipole layer is 11~20%, the weight/mass percentage composition ratio of tin element and phosphide element is 0.004~0.017.The presence of fluorine-containing dipole layer makes anode surface work content be improved.
Description
Technical field
The present invention relates to electronic device association area, more particularly to a kind of organic electroluminescence device.
Background technology
At present, in organic semiconductor industry, organic electroluminescence device (OLED) has brightness height, material selection range
Wide, driving voltage is low, all solidstate actively characteristic such as luminous, while possess high-resolution, wide viewing angle, and fast response time etc. is excellent
Gesture, is the Display Technique and light source of a kind of great potential, meets the development trend of information age mobile communication and presentation of information, with
And the requirement of green lighting technique, it is the focal point of current lot of domestic and foreign researcher.
In the structure of organic electroluminescence device, anode carries current-carrying as a pith of device architecture
The effect that son injection and circuit are connected, and the injection of carrier has with electrode with the interface potential barrier between organic material simultaneously
Close.Anode is typically all to undertake the effect that hole is injected, the conductive oxide film generally used such as tin indium oxide (ITO) etc.,
Its work content only has 4.7eV, and the organic hole transport material used, and its HOMO energy level so causes sky generally in 5.1V or so
Cave injection needs to overcome larger potential barrier, so as to cause hole injection efficiency not high.ITO work content is improved, will be greatly facilitated
Improve the injection efficiency in hole.It is general at present by reduce the Sn/In of ITO surface-elements than or improve containing for surface oxygen atoms
Measure to realize the purpose of raising work content, in addition, can also reach this effect in anode surface formation dipole layer.
The content of the invention
In order to solve the above technical problems, the present invention is intended to provide a kind of modification indium-tin oxide anode and preparation method thereof, is somebody's turn to do
Method makes indium tin oxide films surface form fluorine-containing dipole layer, carried by the way that indium-tin oxide anode surface is carried out into moditied processing
High anode surface work content, so that the anode is greatly improved the injection efficiency in hole in the application, improves the luminous effect of device
Rate.Present invention also offers the organic electroluminescence device for including above-mentioned modification indium-tin oxide anode.
In a first aspect, modifying indium-tin oxide anode, including indium-tin oxide anode and decorative layer, institute the invention provides one kind
Stating indium-tin oxide anode includes glass substrate and the indium tin oxide films for being arranged on the glass baseplate surface, and the decorative layer is set
Put on the indium tin oxide films surface, the decorative layer for indium and fluorine the bonding formation on the indium tin oxide films surface with
The fluorine-containing dipole layer that In-F forms are present, the weight/mass percentage composition of the fluorine element of the fluorine-containing dipole layer is 11~20%, tin member
The weight/mass percentage composition ratio of element and phosphide element is 0.004~0.017.
Preferably, the thickness of the indium tin oxide films is 70~200nm.
Second aspect, the invention provides a kind of preparation method for modifying indium-tin oxide anode, comprises the following steps：
The indium-tin oxide anode includes glass substrate and is arranged on the indium tin oxide films of the glass baseplate surface；
The indium-tin oxide anode is immersed in the fluorine-containing aqueous solutions of organic acids that concentration is 0.2~2mol/L, in 5~20
After being soaked 0.5~2 minute at DEG C, take out, dry；
The dried indium-tin oxide anode is placed in plasma apparatus, fluoro-gas is passed through, makes plasma
Gas pressure in equipment is 10Pa~60Pa, and adjustment radio-frequency power is 40w~100w, carries out 5~10 points of corona treatment
Clock, obtains modifying indium-tin oxide anode, the surface of the modification indium-tin oxide anode has decorative layer, and the decorative layer is described
The indium on indium tin oxide films surface and the fluorine-containing dipole layer existed in In-F forms of fluorine bonding formation.
The percentage composition of the fluorine element of the fluorine-containing dipole layer is 11~20%, and the quality percentage of tin element and phosphide element contains
Amount is than being 0.004~0.017.
The indium-tin oxide anode includes glass substrate and is arranged on the indium tin oxide films of the glass baseplate surface.Adopt
Prepared with following manner：Clean glass substrate is provided, preparation oxidation is sputtered on the glass substrate using magnetron sputtering method
Indium tin thin film.
The glass substrate is commercially available simple glass.
Preferably, the cleaning operation of the glass substrate is specially：Successively using liquid detergent, deionized water, isopropanol and
Acetone carries out being cleaned by ultrasonic 20 minutes respectively, then nitrogen drying.
Preferably, the thickness of the indium tin oxide films is 70~200nm.
The indium-tin oxide anode is immersed in the fluorine-containing aqueous solutions of organic acids that concentration is 0.2~2mol/L, in 5~20 DEG C
After lower immersion 0.5~2 minute, take out, dry.
Preferably, the fluorine-containing organic acid is difluoroacetic acid, trifluoroacetic acid or 2,2- difluoro propionic acid.
Preferably, the concentration of the fluorine-containing aqueous solutions of organic acids is 0.5~1mol/L.
The concrete mode of the drying is not done specifically limited.Preferably, the drying process is：In 50~80 DEG C of vacuum
Dry 12~24 hours.
After pretreatment of the indium-tin oxide anode by fluorine-containing organic acid, its adsorption has a large amount of functional fluoropolymer bases
Group, because fluorine has a strong electron-withdrawing power, therefore these functional fluoropolymer groups will be formed with indium In on tin indium oxide (ITO) surface
Part In-F keys so that the part Sn on tin indium oxide (ITO) surface is replaced by F, but the In-F keys now formed be not it is very stable,
It need to be further processed.
The dried indium-tin oxide anode is placed in plasma apparatus, fluoro-gas is passed through and carries out plasma
Processing, obtains modifying indium-tin oxide anode.The surface of the modification indium-tin oxide anode has decorative layer, and the decorative layer is described
The fluorine-containing dipole layer existed in In-F forms of In and F the bonding formation on indium tin oxide films surface.
Preferably, the fluoro-gas is carbon tetrafluoride or borontrifluoride carbon.
In plasma treatment procedure, gas pressure in plasma apparatus is 10~60Pa, radio-frequency power is 40~
100w, the time of corona treatment is 5~10 minutes.
Indium-tin oxide anode will become more stable unstable In-F keys after fluoro-gas corona treatment；
Meanwhile, indium (In) the formation In-F keys that fluorine in fluoro-gas also can be with ITO surfaces, make the tin (Sn) on ITO surfaces further by
Fluorine (F) replaces；In addition, adsorbing the functional fluoropolymer group not with ITO bondings on surface after fluorine-containing organic low-kappa number
In-F keys will be formed with In, so as to further increase the In-F key ratios on ITO surfaces, the hundred of anode surface element F are improved
Divide content, reduce the Sn/In constituent contents ratio of anode surface.So, will be formd on anode ITO surfaces one layer with
The fluorine-containing dipole layer that In-F forms are present, the percentage composition of the fluorine element of the fluorine-containing dipole layer is 11~20%, tin element and indium
The weight/mass percentage composition ratio of element is 0.004~0.017, accordingly, with respect to common unmodified ito anode, the fluorine-containing dipole
Layer can improve ito anode surface work content as decorative layer presence, so as to reduce the potential barrier that hole injection needs to overcome, improve hole
Injection efficiency.This is due to that the presence of dipole layer will improve the vacuum level E on ITO surfacesvac, a numerical value δ is improved, is so made
The fermi level E of anodeFWith vacuum level EvacDifference DELTA E δs many compared to original difference.According to the definition of work content, work content
It is the difference of material fermi level and vacuum level, so means that work content improves δ numerical value.The presence of i.e. fluorine-containing dipole layer
Improve anode surface work content.
The modification indium-tin oxide anode should be preserved properly, and Conservation environment is vacuum environment ＜ 10-3Pa or guarantor
There is N2In glove box.
The third aspect, the invention provides a kind of organic electroluminescence device, including anode, functional layer, luminescent layer and the moon
Pole, the anode is modification indium-tin oxide anode, and the modification indium-tin oxide anode includes indium-tin oxide anode and decorative layer, institute
Stating indium-tin oxide anode includes glass substrate and the indium tin oxide films for being arranged on the glass baseplate surface, and the decorative layer is set
Put on the indium tin oxide films surface, the decorative layer for indium and fluorine the bonding formation on the indium tin oxide films surface with
The fluorine-containing dipole layer that In-F forms are present, the weight/mass percentage composition of the fluorine element of the fluorine-containing dipole layer is 11~20%, tin member
The weight/mass percentage composition ratio of element and phosphide element is 0.004~0.017.
Preferably, the thickness of the indium tin oxide films is 70~200nm.
Wherein, the functional layer is included in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer extremely
Few one kind.
When the functional layer is multilayer, the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electronics
Implanted layer and negative electrode are successively set on the ito thin film surface of modification indium-tin oxide anode in order.
The material of the hole injection layer can be Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), phthalein
Cyanines oxygen titanium (TiOPc), phthalocyanine platinum (PtPc) or 4,4 ', 4 "-three (N-3- methylphenyl-N-phenyls amino) triphenylamine (m-
MTDATA).The thickness of hole injection layer is 10~40nm.
The hole mobile material of the hole transmission layer can be N, N '-diphenyl-N, N '-two (3- aminomethyl phenyls) -1,
1 '-biphenyl -4,4 '-diamines (TPD), N, N, N ', N '-(tetramethoxy phenyl)-benzidine (MeO-TPD), 2,7- are double
(N, N- bis- (4- methoxyphenyls) amino)-fluorenes of 9,9- spiral shells two (MeO-Sprio-TPD), N, N '-(the 1- naphthalenes of diphenyl-N, N '-two
Base) -1,1 '-biphenyl -4,4 '-diamines (NPB), 1,1- bis- (4- (N, N '-two (p- tolyls) amino) phenyl) hexamethylene
(TAPC) or 2,2 ', 7,7 '-four (N, N- hexichol amidos) -9, the fluorenes of 9 '-spiral shell two (S-TAD), the thickness of hole transmission layer for 20~
50nm。
The material of the luminescent layer is the mixing material of luminescent material doping hole mobile material or electron transport material formation
Material.
The luminescent material can be 4- (dintrile methyl) -2- butyl -6- (the long Lip river pyridine -9- second of 1,1,7,7- tetramethyl
Alkenyl) -4H- pyrans (DCJTB), 2,3,6,7- tetrahydrochysenes -1,1,7,7- tetramethyl -1H, 5H, 11H-10- (2-[4-morpholinodithio base) -
Quinolizino [9,9A, 1GH] cumarin (C545T), two (2- methyl -8-hydroxyquinoline)-(4- xenols) aluminium (BALQ), 4- (two
Nitrile methene) -2- isopropyls -6- (the long Lip river pyridine -9- vinyl of 1,1,7,7- tetramethyl) -4H- pyrans (DCJTI), dimethyl
Quinacridone (DMQA), 8-hydroxyquinoline aluminium (Alq3), 5,6,11,12- tetraphenyl naphthonaphthalenes (Rubrene), 4,4 '-two (2,
2- diphenylethyllenes) -1,1 '-biphenyl (DPVBi), double (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics close iridium (FIrpic),
Double (4,6- difluorophenyl pyridinatos)-four (1- pyrazolyls) boric acid close iridium (FIr6), it is double (4,6- bis- fluoro- 5- cyano-phenyls pyridine-N,
C2) pyridine carboxylic acid close iridium (FCNIrpic), two (2 ', 4 '-difluorophenyl) pyridines] (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 isoquinolins quinoline) (acetyl
Acetone) close iridium (Ir (piq) 2 (acac)), acetopyruvic acid two (2- phenylpyridines) iridium (Ir (ppy) 2 (acac)), three (1- benzene
Base-isoquinolin) close iridium (Ir (piq) 3) or three (2- phenylpyridines) close one or more in iridium (Ir (ppy) 3).Luminescent layer
Thickness is 10~20nm.
The electron transport material of the electron transfer layer can be 2- (4- xenyls) -5- (the 4- tert-butyl groups) phenyl -1,3,
4- oxadiazoles (PBD), (8-hydroxyquinoline)-aluminium (Alq3), 4,7- diphenyl-o-phenanthroline (Bphen), 1,3,5- tri- (1- benzene
Base -1H- benzimidazolyl-2 radicals-yl) benzene (TPBI), 2,9- dimethyl -4,7- biphenyl -1,10- phenanthrolenes (BCP), 1,2,4-
Triazole derivative (such as TAZ) or double (2- methyl -8-hydroxyquinoline-N1, O8)-(1,1 '-biphenyl -4- hydroxyls) aluminium (BAlq).Electronics
The thickness of transport layer is 30~60nm.
The material of the electron injecting layer can be LiF, CsF or NaF, and thickness is 1nm；
The negative electrode can use Ag, Al, Sm, Yb, Mg-Ag alloys or Mg-Al alloys, and thickness is 70~200nm.
Above-mentioned hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode can be used
The mode of vacuum evaporation is sequentially prepared in modification indium-tin oxide anode.
Implement the embodiment of the present invention, have the advantages that：
(1) preparation method for the modification indium-tin oxide anode that the present invention is provided, fluorine-containing by the way that indium-tin oxide anode is carried out
Organic low-kappa number and fluoro-gas corona treatment, reduces the Sn/In constituent contents ratio of anode surface, while making oxidation
Indium tin anode surface forms decorative layer, i.e., the fluorine-containing dipole layer existed in the form of In-F, so as to improve anode surface work(
Letter；
(2) preparation method for the modification indium-tin oxide anode that the present invention is provided, technique is simple, and cost is low；
(3) the modification indium-tin oxide anode that provides of the present invention, can be widely applied to organic electroluminescence device and it is organic too
In positive energy battery, the efficiency of device is improved.
Brief description of the drawings
Fig. 1 is the structure chart for the organic electroluminescence device that the embodiment of the present invention 1 is provided；
Fig. 2 is the electric current of organic electroluminescence device and existing organic electroluminescence device that the embodiment of the present invention 4 is provided
The graph of a relation of density and voltage.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Embodiment 1
A kind of preparation method for modifying indium-tin oxide anode, comprises the following steps：
(1) glass substrate is taken, ultrasonic cleaning 20 is carried out using liquid detergent, deionized water, isopropanol and acetone respectively successively
Minute, then nitrogen is dried up；Use magnetron sputtering method to prepare indium tin oxide films of the thickness for 100nm on the glass substrate, obtain
To indium-tin oxide anode；
(2) indium-tin oxide anode is immersed in the difluoroacetic acid aqueous solution that concentration is 2mol/L, in immersion at 10 DEG C
After 0.5 minute, take out, 50 DEG C are dried in vacuo 12 hours；
(3) dried indium-tin oxide anode is placed in plasma apparatus, is passed through carbon tetrafluoride (CF4) gas progress
Corona treatment, obtains modifying indium-tin oxide anode, the surface of modification indium-tin oxide anode has decorative layer, and decorative layer is oxygen
Change the fluorine-containing dipole layer existed in In-F forms of In and F the bonding formation on indium tin thin film surface.
In plasma treatment procedure, gas pressure in plasma apparatus is 10Pa, and radio-frequency power is 50w, wait from
The time of daughter processing is 6 minutes.
The obtained modification indium-tin oxide anode of the present embodiment, its finishing coat is the fluorine-containing idol existed in the form of In-F
Pole layer, the dipole layer will improve the vacuum level E on ITO surfacesvac, a numerical value δ is improved, so makes the fermi level E of anodeF
With vacuum level EvacDifference DELTA E δs many compared to original difference.According to the definition of work content, work content be material fermi level with
The difference of vacuum level, so means that work content improves δ numerical value.The surface work content one of unmodified indium-tin oxide anode
As be 4.7eV, the surface work content of the modification indium-tin oxide anode that the present embodiment is prepared is 5.7eV.
Embodiment 2
A kind of preparation method for modifying indium-tin oxide anode, comprises the following steps：
(1) glass substrate is taken, ultrasonic cleaning 20 is carried out using liquid detergent, deionized water, isopropanol and acetone respectively successively
Minute, then nitrogen is dried up；Use magnetron sputtering method to prepare indium tin oxide films of the thickness for 70nm on the glass substrate, obtain
Indium-tin oxide anode；
(2) indium-tin oxide anode is immersed in the trifluoroacetic acid aqueous solution that concentration is 0.2mol/L, in 2 points of immersion at 20 DEG C
Zhong Hou, takes out, and 80 DEG C are dried in vacuo 12 hours；
(3) dried indium-tin oxide anode is placed in plasma apparatus, is passed through borontrifluoride carbon (CHF3) gas enters
Row corona treatment, obtains modifying indium-tin oxide anode, the surface of modification indium-tin oxide anode has decorative layer, and decorative layer is
The fluorine-containing dipole layer existed in In-F forms of In and F the bonding formation on indium tin oxide films surface.
In plasma treatment procedure, gas pressure in plasma apparatus is 30Pa, and radio-frequency power is 40w, wait from
The time of daughter processing is 10 minutes.
The surface work content for the modification indium-tin oxide anode that the present embodiment is prepared is 5.8eV.
Embodiment 3
A kind of preparation method for modifying indium-tin oxide anode, comprises the following steps：
(1) glass substrate is taken, ultrasonic cleaning 20 is carried out using liquid detergent, deionized water, isopropanol and acetone respectively successively
Minute, then nitrogen is dried up；Use magnetron sputtering method to prepare indium tin oxide films of the thickness for 200nm on the glass substrate, obtain
To indium-tin oxide anode；
(2) indium-tin oxide anode is immersed into concentration in 1mol/L 2, the 2- difluoro propionic acid aqueous solution, in soaking 1 at 5 DEG C
After minute, take out, 60 DEG C are dried in vacuo 24 hours；
(3) dried indium-tin oxide anode is placed in plasma apparatus, is passed through carbon tetrafluoride (CF4) gas progress
Corona treatment, obtains modifying indium-tin oxide anode, the surface of modification indium-tin oxide anode has decorative layer, and decorative layer is oxygen
Change the fluorine-containing dipole layer existed in In-F forms of In and F the bonding formation on indium tin thin film surface.
In plasma treatment procedure, the gas pressure in plasma processing chamber is 60Pa, and radio-frequency power is 100w,
The time of corona treatment is 5 minutes.
The surface work content for the modification indium-tin oxide anode that the present embodiment is prepared is 5.9eV.
By the gained of the above embodiment of the present invention 1~3 modification indium-tin oxide anode and unmodified common tin indium oxide
Anode carries out surface-element analysis, and method of testing uses XPS (x-ray photoelectron spectroscopy), and INSTRUMENT MODEL is ESCA2000 (VG
Microtech Inc. companies), test condition is that ray energy is 1486.6eV using Al target K alpha rays source.ITO is calculated respectively
The 1s tracks of film surface C element, the 3d of In elements5/2Track, the 3d of Sn elements5/2The 1s tracks of track O elements, F elements
1s tracks, calculate each element percentage composition, and its testing result is as shown in table 1.
Table 1
From table 1 it follows that unmodified common indium-tin oxide anode, its surface is by C, O, In, tetra- kinds of elements of Sn
Composition, the modification indium-tin oxide anode after the inventive method moditied processing, many F elements in surface illustrates at process modification
Reason, F elements are formed on ito thin film surface with In bondings, so as to be formd on ito thin film surface with the fluorine-containing of In-F forms presence
Dipole layer.Modification indium-tin oxide anode prepared by the present invention, its fluorine-contained surface dipole are can be seen that from Elemental analysis data result
The percentage composition of the F elements of layer has reached more than 11%, has been up to 19.46%.Simultaneously at the modification by the present invention
Reason, the Sn/In ratios on ITO surfaces are greatly reduced, and minimum 0.004 is fallen below from 0.188.Illustrate that F instead of part Sn key mapping, with
In bondings.
Embodiment 4
A kind of organic electroluminescence device, including stack gradually anode, hole injection layer, hole transmission layer, luminescent layer,
Electron transfer layer, electron injecting layer and negative electrode, the anode are modification indium-tin oxide anode prepared by the embodiment of the present invention 1.
Specifically, in the present embodiment, the material of hole injection layer is Phthalocyanine Zinc (ZnPc), and thickness is 15nm；Hole transport
The material of layer is N, N '-diphenyl-N, N '-two (3- aminomethyl phenyls) -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) doping 8% mass fraction 1,3,5- tri- (1- benzene
Base -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi) formation mixing material, 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-yl) benzene (TPBi), thickness
For 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 organic electroluminescent
The structure of device includes, modify 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, modification ito anode 10 includes ito anode 101 and decorative layer 102, the decorative layer
102 be the presence of fluorine-containing dipole layer in the form of In-F.
Compared with existing organic electroluminescence device, organic electroluminescence device of the embodiment of the present invention is as a result of modification
Indium-tin oxide anode, anode surface work content is improved, and hole injection efficiency is improved, so that the startup voltage of device is bright
Aobvious reduction.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).Existing organic electroluminescence device is opened
Dynamic voltage is 3.0eV, and the startup voltage 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 relation of voltage
Figure.Wherein, curve 1 is the current density of the present embodiment organic electroluminescence device and the graph of a relation of voltage；Curve 2 has to be existing
The current density of organic electroluminescence devices and the graph of a relation of voltage.It can be seen that starting in identical under voltage, this reality
Higher Injection Current can be obtained by applying an organic electroluminescence device, so that device has higher luminous efficiency.It is existing to have
The luminous efficiency of organic electroluminescence devices is 13.11m/W, and the luminous efficiency of the present embodiment organic electroluminescence device is
26.41m/W.This is due to that the present embodiment organic electroluminescence device employs modification indium-tin oxide anode, improves hole
Injection efficiency, therefore, it is possible to obtain higher Carrier Injection Efficiency, improves device organic electroluminescent efficiency.
Embodiment 5
A kind of organic electroluminescence device, including stack gradually anode, hole injection layer, hole transmission layer, luminescent layer,
Electron transfer layer, electron injecting layer and negative electrode, the anode are modification indium-tin oxide anode prepared by the embodiment of the present invention 2.Institute
The material and embodiment 4 for stating hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are same.
The startup voltage of the present embodiment organic electroluminescence device is 2.1eV, and luminous efficiency is 31.11m/w.
Embodiment 6
A kind of organic electroluminescence device, including stack gradually anode, hole injection layer, hole transmission layer, luminescent layer,
Electron transfer layer, electron injecting layer and negative electrode, the anode are modification indium-tin oxide anode prepared by the embodiment of the present invention 3.Institute
The material and embodiment 4 for stating hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are same.
The startup voltage of the present embodiment organic electroluminescence device is 2.0eV, and luminous efficiency is 35.21m/w.
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (10)
1. a kind of organic electroluminescence device, including anode, functional layer, luminescent layer and negative electrode, the anode are modification indium oxide
Tin anode, the modification indium-tin oxide anode includes indium-tin oxide anode and decorative layer, and the indium-tin oxide anode includes glass
Substrate and the indium tin oxide films for being arranged on the glass baseplate surface, the decorative layer are arranged on the indium tin oxide films table
Face, the fluorine-containing dipole existed in In-F forms that the decorative layer is formed for the indium on the indium tin oxide films surface with fluorine bonding
Layer, the weight/mass percentage composition of the fluorine element of the fluorine-containing dipole layer is 11~20%, and the quality percentage of tin element and phosphide element contains
Amount is than being 0.004~0.017；The modification indium-tin oxide anode is prepared from using following steps：
Clean indium-tin oxide anode is provided；The indium-tin oxide anode includes glass substrate and is arranged on the glass substrate table
The indium tin oxide films in face；
The indium-tin oxide anode is immersed in the fluorine-containing aqueous solutions of organic acids that concentration is 0.2~2mol/L, in leaching at 5~20 DEG C
Bubble takes out after 0.5~2 minute, dries；
The dried indium-tin oxide anode is placed in plasma apparatus, fluoro-gas is passed through, makes plasma apparatus
Interior gas pressure is 10Pa~60Pa, and adjustment radio-frequency power is 40w~100w, carries out corona treatment 5~10 minutes, obtains
To modification indium-tin oxide anode, the surface of the modification indium-tin oxide anode has decorative layer, and the decorative layer is the oxidation
The indium on indium tin thin film surface and the fluorine-containing dipole layer existed in In-F forms of fluorine bonding formation.
2. organic electroluminescence device as claimed in claim 1, it is characterised in that the thickness of the indium tin oxide films is 70
~200nm.
3. organic electroluminescence device as claimed in claim 1, it is characterised in that the functional layer include hole injection layer,
At least one of hole transmission layer, electron transfer layer and electron injecting layer.
4. organic electroluminescence device as claimed in claim 3, it is characterised in that described when the functional layer is multilayer
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are successively set on modification in order
The ito thin film surface of indium-tin oxide anode.
5. organic electroluminescence device as claimed in claim 3, it is characterised in that the material of the 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-phenyls amino) triphenylamine (m-MTDATA), the thickness of hole injection layer is 10~40nm.
6. organic electroluminescence device as claimed in claim 3, it is characterised in that the hole transport material of the hole transmission layer
Expect can be N, N '-diphenyl-N, N '-two (3- aminomethyl phenyls) -1,1 '-biphenyl -4,4 '-diamines (TPD), N, N, N ', N ' -
Double (N, N- bis- (4- methoxyphenyls) amino) -9, the 9- spiral shells of (tetramethoxy phenyl)-benzidine (MeO-TPD), 2,7-
Two fluorenes (MeO-Sprio-TPD), N, N '-diphenyl-N, N '-two (1- naphthyls) -1,1 '-biphenyl -4,4 '-diamines (NPB), 1,1-
Two (4- (N, N '-two (p- tolyls) amino) phenyl) hexamethylenes (TAPC) or 2,2 ', 7,7 '-four (N, N- hexichol amidos) -9,
The fluorenes of 9 '-spiral shell two (S-TAD), the thickness of hole transmission layer is 20~50nm.
7. organic electroluminescence device as claimed in claim 1, it is characterised in that the material of the luminescent layer is luminescent material
Doping hole mobile material or the mixing material of electron transport material formation.
8. organic electroluminescence device as claimed in claim 7, it is characterised in that the luminescent material can be 4- (dintrile
Methyl) -2- butyl -6- (the long Lip river pyridine -9- vinyl of 1,1,7,7- tetramethyl) -4H- pyrans (DCJTB), 2,3,6,7- tetrahydrochysenes -
1,1,7,7- tetramethyl -1H, 5H, 11H-10- (2-[4-morpholinodithio base)-quinolizino [9,9A, 1GH] cumarin (C545T), two
(2- methyl -8-hydroxyquinoline)-(4- xenols) aluminium (BALQ), 4- (dintrile methene) -2- isopropyls -6- (1,1,7,7- tetra-
The long Lip river pyridine -9- vinyl of methyl) -4H- pyrans (DCJTI), dimethylquinacridone (DMQA), 8-hydroxyquinoline aluminium
(Alq3), 5,6,11,12- tetraphenyl naphthonaphthalenes (Rubrene), 4,4 '-two (2,2- diphenylethyllene) -1,1 '-biphenyl
(DPVBi), double (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics close iridium (FIrpic), double (4,6- difluorophenyl pyridinatos)-four
(1- pyrazolyls) boric acid closes iridium (FIr6), double (4,6- bis- fluoro- 5- cyano-phenyls pyridine-N, C2) pyridine carboxylic acids and 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 isoquinolins quinoline) (acetylacetone,2,4-pentanediones) and close iridium (Ir (piq) 2
(acac)), acetopyruvic acid two (2- phenylpyridines) iridium (Ir (ppy) 2 (acac)), three (1- phenyl-isoquinolin) close iridium (Ir
(piq) 3) or three (2- phenylpyridines) close the one or more in iridium (Ir (ppy) 3), the thickness of luminescent layer is 10~20nm.
9. organic electroluminescence device as claimed in claim 3, it is characterised in that the electric transmission material of the electron transfer layer
Material can be 2- (4- xenyls) -5- (the 4- tert-butyl groups) phenyl -1,3,4- oxadiazoles (PBD), (8-hydroxyquinoline)-aluminium
(Alq3), 4,7- diphenyl-o-phenanthroline (Bphen), 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi),
2,9- dimethyl -4,7- biphenyl -1,10- phenanthrolenes (BCP), 1,2,4- triazole derivatives or double (2- methyl -8- hydroxyl quinolines
Quinoline-N1, O8)-(1,1 '-biphenyl -4- hydroxyls) aluminium (BAlq), the thickness of electron transfer layer is 30~60nm.
10. organic electroluminescence device as claimed in claim 3, it is characterised in that above-mentioned hole injection layer, hole transport
Layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode can be sequentially prepared by the way of vacuum evaporation in modification oxidation
On indium tin anode.
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| WO1999039393A1 (en) * | 1998-02-02 | 1999-08-05 | International Business Machines Corporation | Anode modification for organic light emitting diodes |
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| KR100289649B1 (en) * | 1998-06-25 | 2001-05-02 | 박종섭 | Manufacturing Method of Thin Film Transistor Liquid Crystal Display Device |
| CN101179114A (en) * | 2007-12-10 | 2008-05-14 | 天津理工大学 | Flexible organic electroluminescent device and method of producing the same |
| CN202308074U (en) * | 2011-09-08 | 2012-07-04 | 深圳市创益科技发展有限公司 | Organic solar battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999039393A1 (en) * | 1998-02-02 | 1999-08-05 | International Business Machines Corporation | Anode modification for organic light emitting diodes |
| US6208075B1 (en) * | 1998-11-05 | 2001-03-27 | Eastman Kodak Company | Conductive fluorocarbon polymer and method of making same |
| CN1983664A (en) * | 2005-12-14 | 2007-06-20 | 中国科学院化学研究所 | Organic LED based on anode modification |
| CN101123299A (en) * | 2007-08-31 | 2008-02-13 | 吉林大学 | A blue light top radiation organic EL part |
| CN102610725A (en) * | 2012-03-29 | 2012-07-25 | 华北电力大学 | Semiconductor quantum dot light-emitting diode and preparing method thereof |
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| CN105895824A (en) | 2016-08-24 |
| CN103928628B (en) | 2016-10-05 |
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