CN104183755A - White-light organic light-emitting device and preparation method thereof - Google Patents
White-light organic light-emitting device and preparation method thereof Download PDFInfo
- Publication number
- CN104183755A CN104183755A CN201310192553.7A CN201310192553A CN104183755A CN 104183755 A CN104183755 A CN 104183755A CN 201310192553 A CN201310192553 A CN 201310192553A CN 104183755 A CN104183755 A CN 104183755A
- Authority
- CN
- China
- Prior art keywords
- layer
- bis
- phenyl
- blue
- carbazole
- 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.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000009467 reduction Effects 0.000 claims abstract description 112
- 230000005540 biological transmission Effects 0.000 claims abstract description 94
- 238000002347 injection Methods 0.000 claims abstract description 86
- 239000007924 injection Substances 0.000 claims abstract description 86
- 239000011521 glass Substances 0.000 claims abstract description 74
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims description 530
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 140
- 238000001704 evaporation Methods 0.000 claims description 120
- 229910052741 iridium Inorganic materials 0.000 claims description 118
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 118
- 230000008020 evaporation Effects 0.000 claims description 111
- 238000004020 luminiscence type Methods 0.000 claims description 111
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 100
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 80
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 78
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 63
- 239000004305 biphenyl Substances 0.000 claims description 60
- 235000010290 biphenyl Nutrition 0.000 claims description 50
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 42
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims description 38
- 239000002019 doping agent Substances 0.000 claims description 37
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 36
- HSEVUSRQUCWDNF-UHFFFAOYSA-N NCC=1C=C(C=CC1)N(C1=CC=C(C=C1)C1=CC=C(N(C2=CC=CC=C2)C2=CC(=CC=C2)CN)C=C1)C1=CC=CC=C1 Chemical compound NCC=1C=C(C=CC1)N(C1=CC=C(C=C1)C1=CC=C(N(C2=CC=CC=C2)C2=CC(=CC=C2)CN)C=C1)C1=CC=CC=C1 HSEVUSRQUCWDNF-UHFFFAOYSA-N 0.000 claims description 35
- 239000004411 aluminium Substances 0.000 claims description 35
- 229910052782 aluminium Inorganic materials 0.000 claims description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 35
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 35
- -1 4, 6-difluorophenyl Chemical group 0.000 claims description 34
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 34
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 34
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 34
- 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 34
- IYVKASORLNOINI-UHFFFAOYSA-N 9-(3-pyridin-2-ylphenyl)carbazole Chemical class N1=CC=CC=C1C1=CC=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=C1 IYVKASORLNOINI-UHFFFAOYSA-N 0.000 claims description 32
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical compound O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 claims description 31
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 28
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 20
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical class C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 claims description 18
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 16
- VOIVTTPPKHORBL-UHFFFAOYSA-N 1-naphthalen-1-ylanthracene Chemical class C1=CC=C2C(C=3C4=CC5=CC=CC=C5C=C4C=CC=3)=CC=CC2=C1 VOIVTTPPKHORBL-UHFFFAOYSA-N 0.000 claims description 16
- FHGGUWFGLZJGDB-UHFFFAOYSA-N C1=CC=CC=C1.C1(=CC=CC=C1)[Si](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1=CC=CC=C1.C1(=CC=CC=C1)[Si](C1=CC=CC=C1)C1=CC=CC=C1 FHGGUWFGLZJGDB-UHFFFAOYSA-N 0.000 claims description 16
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical group C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 14
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 14
- KZULYCPTNSEXTR-UHFFFAOYSA-N 2-(2,4-difluorophenyl)pyridine 2-[5-(trifluoromethyl)-1H-1,2,4-triazol-3-yl]pyridine Chemical compound FC(C1=NNC(=N1)C1=NC=CC=C1)(F)F.FC1=CC=C(C(=C1)F)C1=NC=CC=C1 KZULYCPTNSEXTR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 11
- 229920003023 plastic Polymers 0.000 claims description 11
- LPCWDYWZIWDTCV-UHFFFAOYSA-N 1-phenylisoquinoline Chemical compound C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 LPCWDYWZIWDTCV-UHFFFAOYSA-N 0.000 claims description 10
- 239000005083 Zinc sulfide Substances 0.000 claims description 10
- 238000001994 activation Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 229910003437 indium oxide Inorganic materials 0.000 claims description 10
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000003599 detergent Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 9
- 229910001887 tin oxide Inorganic materials 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 8
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 claims description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 7
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 7
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-phenyl-5-(4-phenylphenyl)-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=C(C=2C=CC=CC=2)C=C1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 claims description 6
- MJHALVMQSVRHLU-UHFFFAOYSA-N N1=C(C=CC=C1)C1=NN=NN1.FC1=CC=C(C(=C1)F)C1=NC=CC=C1 Chemical compound N1=C(C=CC=C1)C1=NN=NN1.FC1=CC=C(C(=C1)F)C1=NC=CC=C1 MJHALVMQSVRHLU-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 6
- AYTVLULEEPNWAX-UHFFFAOYSA-N cesium;azide Chemical compound [Cs+].[N-]=[N+]=[N-] AYTVLULEEPNWAX-UHFFFAOYSA-N 0.000 claims description 6
- RTRAMYYYHJZWQK-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1 RTRAMYYYHJZWQK-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 description 136
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 63
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 48
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 48
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 48
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 25
- 239000002585 base Substances 0.000 description 24
- DETFWTCLAIIJRZ-UHFFFAOYSA-N triphenyl-(4-triphenylsilylphenyl)silane Chemical compound C1=CC=CC=C1[Si](C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 DETFWTCLAIIJRZ-UHFFFAOYSA-N 0.000 description 20
- 229910016460 CzSi Inorganic materials 0.000 description 18
- WIHKEPSYODOQJR-UHFFFAOYSA-N [9-(4-tert-butylphenyl)-6-triphenylsilylcarbazol-3-yl]-triphenylsilane Chemical compound C1=CC(C(C)(C)C)=CC=C1N1C2=CC=C([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)C=C2C2=CC([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=C21 WIHKEPSYODOQJR-UHFFFAOYSA-N 0.000 description 18
- 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 description 18
- 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 description 17
- 239000004814 polyurethane Substances 0.000 description 17
- 229920002635 polyurethane Polymers 0.000 description 16
- YERGTYJYQCLVDM-UHFFFAOYSA-N iridium(3+);2-(4-methylphenyl)pyridine Chemical compound [Ir+3].C1=CC(C)=CC=C1C1=CC=CC=N1.C1=CC(C)=CC=C1C1=CC=CC=N1.C1=CC(C)=CC=C1C1=CC=CC=N1 YERGTYJYQCLVDM-UHFFFAOYSA-N 0.000 description 15
- 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 description 14
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000005401 electroluminescence Methods 0.000 description 12
- SSABEFIRGJISFH-UHFFFAOYSA-N 2-(2,4-difluorophenyl)pyridine Chemical class FC1=CC(F)=CC=C1C1=CC=CC=N1 SSABEFIRGJISFH-UHFFFAOYSA-N 0.000 description 10
- 239000004642 Polyimide Substances 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- 239000004033 plastic Substances 0.000 description 7
- LQWXEEDCMLEVHU-UHFFFAOYSA-N 2-(2h-tetrazol-5-yl)pyridine Chemical compound N1=CC=CC=C1C1=NNN=N1 LQWXEEDCMLEVHU-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 150000003222 pyridines Chemical class 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- SYOANZBNGDEJFH-UHFFFAOYSA-N 2,5-dihydro-1h-triazole Chemical compound C1NNN=C1 SYOANZBNGDEJFH-UHFFFAOYSA-N 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001556 benzimidazoles Chemical class 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- QWODREODAXFISP-UHFFFAOYSA-N n-[4-(4-anilinophenyl)phenyl]-n-phenylnaphthalen-1-amine Chemical compound C=1C=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=CC=1NC1=CC=CC=C1 QWODREODAXFISP-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 210000001072 colon Anatomy 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001771 vacuum deposition 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
- H10K50/80—Constructional details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/155—Hole transporting layers comprising dopants
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Disclosed is a white-light organic light-emitting device which includes an anode, a first hole injection layer, a first hole transmission layer, a first light-emitting unit, a first electron transmission layer, a charge generation layer, a second hole injection layer, a second hole transmission layer, a second light-emitting unit, a second electron transmission layer, an electron injection layer and a cathode, which are sequentially laminated. The anode includes a first anti-reflection layer, a glass substrate, a second anti-reflection layer, a refraction layer, a transparent conductive layer, a first short-circuit reduction layer and a second short-circuit reduction layer, which are sequentially laminated. The white-light organic light-emitting device has a comparatively low work current. The invention also provides a preparation method for the white-light organic light-emitting device.
Description
Technical field
The present invention relates to field of electronic devices, particularly a kind of white light organic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) has advantages of that some are unique: (1) OLED belongs to diffused area source, does not need by extra light-conducting system, to obtain large-area white light source as light-emitting diode (LED); (2) due to the diversity of luminous organic material, OLED illumination is the light of design color as required, no matter be little Molecule OLEDs at present, or polymer organic LED (PLED) has all obtained and has comprised white-light spectrum at the light of interior all colours; (3) OLED can make on as glass, pottery, metal, plastic or other material at multiple substrate, freer when this makes to design lighting source; (4) adopt the mode of making OLED demonstration to make OLED illumination panel, can in illumination, show information; (5) OLED also can be used as controlled look in illuminator, allows user to regulate light atmosphere according to individual demand.But there is the problem that color rendering index is lower, operating current is larger in traditional organic electroluminescence device.
Summary of the invention
Given this, be necessary to provide white light organic electroluminescent device that a kind of operating current is less and preparation method thereof.
A white light organic electroluminescent device, comprises the anode, the first hole injection layer, the first hole transmission layer, the first luminescence unit, the first electron transfer layer, charge generation layer, the second hole injection layer, the second hole transmission layer, the second luminescence unit, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described anode comprises the first anti-reflecting layer, glass substrate, the second anti-reflecting layer, dioptric layer, transparency conducting layer, the first short reduction layer and the second short reduction layer stacking gradually, and the material of described the first anti-reflecting layer and described the second anti-reflecting layer is SiGe, described dioptric layer is formed with the projection of a plurality of spaced strips near the surface of described the second anti-reflecting layer, the cross section of described projection is semicircle, the end of described projection and described the second anti-reflecting layer butt and be bonded together, described transparency conducting layer is laminated in described dioptric layer away from a side of described projection, and the material of described the first short reduction layer is SiGe, and the material of described the second short reduction layer is selected from least one of indium oxide, zinc sulphide, tin oxide and silicon dioxide, described the first hole injection layer is laminated on described the second short reduction layer, described the first luminescence unit comprises the first red light luminescent layer, green luminescence layer and the first blue light-emitting stacking gradually, and described the first red light luminescent layer is laminated on described the first hole transmission layer, described the second luminescence unit comprises the second red light luminescent layer and is laminated in the second blue light-emitting on described the second red light luminescent layer, and described the second red light luminescent layer is laminated on described the second hole transmission layer, the material of described the first blue light-emitting comprises the first Blue-light emitting host material, be entrained in the first blue light guest materials and the first charge generating material in described the first Blue-light emitting host material, the mass ratio of described the first blue light guest materials and described the first Blue-light emitting host material is 0.05～0.2:1, the mass ratio of described the first charge generating material and described the first Blue-light emitting host material is 0.05～0.1:1, the material of described the second blue light-emitting comprises the second Blue-light emitting host material, be entrained in the second blue light guest materials and the second charge generating material in described the second Blue-light emitting host material, the mass ratio of described the second blue light guest materials and described the second Blue-light emitting host material is 0.05～0.2:1, the mass ratio of described the second charge generating material and described the second Blue-light emitting host material is 0.05～0.1:1, described the first Blue-light emitting host material and described the second Blue-light emitting host material are selected from 4,4'-bis-(9-carbazole) biphenyl, 9,9'-(1,3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles, 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines, 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine and the Isosorbide-5-Nitraes of 5---at least one in two (triphenyl silicon) benzene, described the first blue light guest materials and described the second blue light guest materials are selected from two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium, two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium and two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) closes at least one in iridium, described the first charge generating material and described the second charge generating material are selected from molybdenum trioxide, tungstic acid, at least one in vanadic oxide and rhenium trioxide,
The material of described charge generation layer is selected from least one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide.
In an embodiment, the material of described dioptric layer is that refractive index is 1.7～1.9 overlay therein; Each protruding diameter is 5 microns～20 microns, and the distance between adjacent two projections is 5 microns～20 microns; Described the first anti-reflecting layer and the second anti-reflecting layer thickness are 10 nanometer～20 nanometers; The material of described transparency conducting layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide, and thickness is 80～150 nanometers; The thickness of described the first short reduction layer and described the second short reduction layer is 2 nanometer～5 nanometers.
Therein in an embodiment, the material of described the first red light luminescent layer comprises the first ruddiness material of main part and is doped in the first ruddiness guest materials in described the first ruddiness material of main part, and the mass ratio of described the first ruddiness guest materials and described the first ruddiness material of main part is 0.005～0.02:1, the material of described the second red light luminescent layer comprises the second ruddiness material of main part and is doped in the second ruddiness guest materials in described the second ruddiness material of main part, and the mass ratio of described the second ruddiness guest materials and described the second ruddiness material of main part is 0.005～0.02:1, described the first ruddiness material of main part and the second ruddiness material of main part are selected from 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] cyclohexane and 9, at least one in two (1-naphthyl) anthracenes of 10-, described the first ruddiness guest materials and the second ruddiness guest materials are selected from two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III), two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) and three (1-phenyl-isoquinolin) and close at least one in iridium,
The material of described green luminescence layer comprises green glow material of main part and is doped in the green glow guest materials in described green glow material of main part, and the mass ratio of described green glow guest materials and described green glow material of main part is 0.02～0.10:1; Described green glow material of main part is selected from 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in two (1-naphthyl) anthracenes of cyclohexane and 9,10-; Described green glow guest materials is selected from that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium and three [2-(p-methylphenyl) pyridine] closes at least one in iridium (III).
In an embodiment, the thickness of described the first red light luminescent layer is 10 nanometer～30 nanometers therein; The thickness of described green luminescence layer is 10 nanometer～30 nanometers; The thickness of described the first blue light-emitting is 5 nanometer～15 nanometers; The thickness of described the second red light luminescent layer is 10 nanometer～30 nanometers; The thickness of described the second blue light-emitting is 5 nanometer～15 nanometers.
Therein in an embodiment, the material of described the first hole injection layer comprises hole mobile material and is doped in the p-type dopant material in described hole mobile material, and the mass ratio of p-type dopant material described in described the first hole injection layer and described hole mobile material is 0.25～0.35:1; The material of described the second hole injection layer comprises hole mobile material and is doped in the p-type dopant material in described hole mobile material, and the mass ratio of p-type dopant material described in described the second hole injection layer and described hole mobile material is 0.25～0.35:1; Described hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane; Described p-type dopant material is selected from least one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide;
The material of the material of described the first hole transmission layer and described the second hole transmission layer is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane;
The material of the material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described electron injecting layer comprises electron transport material and is doped in the N-shaped dopant material in described electron transport material, and the mass ratio of described N-shaped dopant material and described electron transport material is 0.25～0.35:1; Described electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; Described N-shaped dopant material is selected from least one in cesium carbonate, cesium fluoride, cesium azide, lithium carbonate, lithium fluoride and lithia; And
The material of described negative electrode is selected from least one in silver, aluminium and gold.
A preparation method for white light organic electroluminescent device, comprises the steps:
On glass substrate two sides, the first anti-reflecting layer and the second anti-reflecting layer are prepared in sputter respectively;
Dioptric layer is pressed on the second anti-reflecting layer of glass substrate, described dioptric layer is formed with the projection of a plurality of spaced strips near the surface of described the second anti-reflecting layer, the cross section of described projection is semicircle, the end of described projection and described the second anti-reflecting layer butt and be bonded together;
A side surface deposit transparent conductive layer at described dioptric layer away from described projection;
On described transparency conducting layer, magnetron sputtering is prepared the first short reduction layer and the second short reduction layer successively, and described the first anti-reflecting layer, glass substrate, the second anti-reflecting layer, dioptric layer, transparency conducting layer, the first short reduction layer and the second short reduction layer form anode;
On described the second short reduction layer, evaporation is prepared the first hole injection layer and the first hole transmission layer successively;
Evaporation the first luminescence unit on described the first hole transmission layer, described the first luminescence unit comprises the first red light luminescent layer, green luminescence layer and the first blue light-emitting stacking gradually, wherein, the material of described the first blue light-emitting comprises the first Blue-light emitting host material, be entrained in the first blue light guest materials and the first charge generating material in described the first Blue-light emitting host material, the mass ratio of described the first blue light guest materials and described the first Blue-light emitting host material is 0.05～0.2:1, the mass ratio of described the first charge generating material and described the first Blue-light emitting host material is 0.05～0.1:1, described the first Blue-light emitting host material is selected from 4, 4'-bis-(9-carbazole) biphenyl, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-, 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 6-, 3, two (3-(9H-carbazole-9-yl) phenyl) pyridines and 1 of 5-, at least one in two (triphenyl silicon) benzene of 4--, described the first blue light guest materials is selected from two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium, two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium and two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) closes at least one in iridium, described the first charge generating material is selected from molybdenum trioxide, tungstic acid, at least one in vanadic oxide and rhenium trioxide,
At described the first blue light-emitting surface evaporation, prepare the first electron transfer layer;
At described the first electron transfer layer surface evaporation, prepare charge generation layer, the material of described charge generation layer is selected from least one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide;
On described charge generation layer surface, evaporation is prepared the second hole injection layer and the second hole transmission layer;
At described the second hole transmission layer surface evaporation, prepare the second luminescence unit, described the second luminescence unit comprises the second red light luminescent layer and the second blue light-emitting, the material of described the second blue light-emitting comprises the second Blue-light emitting host material, be entrained in the second blue light guest materials and the second charge generating material in described the second Blue-light emitting host material, the mass ratio of described the second blue light guest materials and described the first Blue-light emitting host material is 0.05～0.2:1, the mass ratio of described the second charge generating material and described the second Blue-light emitting host material is 0.05～0.1:1, described the second Blue-light emitting host material is selected from 4, 4'-bis-(9-carbazole) biphenyl, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-, 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 6-, 3, two (3-(9H-carbazole-9-yl) phenyl) pyridines and 1 of 5-, at least one in two (triphenyl silicon) benzene of 4--, described the second blue light guest materials is selected from two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium, two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium and two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) closes at least one in iridium, described the second charge generating material is selected from molybdenum trioxide, tungstic acid, at least one in vanadic oxide and rhenium trioxide, and
On described the second blue light-emitting surface successively evaporation, prepare the second electron transfer layer, electron injecting layer and negative electrode, obtain white light organic electroluminescent device.
Therein in an embodiment, also comprise the step that described glass substrate is cleaned before dioptric layer being pressed on the second anti-reflecting layer of glass substrate; The step of described cleaning is: glass substrate is adopted to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, and then dry, more clean glass substrate is carried out to surface activation process.
Therein in an embodiment, the material of described the first short reduction layer is SiGe, the material of described the second short reduction layer is selected from least one of indium oxide, zinc sulphide, tin oxide and silicon dioxide, and the thickness of described the first short reduction layer and described the second short reduction layer is 2 nanometer～5 nanometers.
Therein in an embodiment, on described the second short reduction layer, evaporation forms before described the first hole injection layer first described anode in 60 ℃～80 ℃ vacuumizes 15 minutes～30 minutes.
In an embodiment, the material of described dioptric layer is that refractive index is 1.7～1.9 transparent plastic therein; Each protruding diameter is 5 microns～20 microns, and the distance between adjacent two projections is 5 microns～20 microns; The material of described transparency conducting layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide.
Above-mentioned white light organic electroluminescent device comprises the anode stacking gradually, the first hole injection layer, the first hole transmission layer, the first luminescence unit, the first electron transfer layer, charge generation layer, the second hole injection layer, the second hole transmission layer, the second luminescence unit, the second electron transfer layer, electron injecting layer and negative electrode, what adopt is PIN laminated construction, and anode comprises the first anti-reflecting layer stacking gradually, glass substrate, the second anti-reflecting layer, dioptric layer, transparency conducting layer, the first short reduction layer and the second short reduction layer, described dioptric layer is formed with the hemispherical projections of a plurality of spaced strips near the surface of described the second anti-reflecting layer, the end of described hemispherical projections and described the second anti-reflecting layer butt and be bonded together, described transparency conducting layer is laminated in described dioptric layer away from a side of described hemispherical projections, the material of described the first short reduction layer is SiGe, the material of described the second short reduction layer is selected from least one of indium oxide, zinc sulphide, tin oxide and silicon dioxide, by new bright dipping mode, adopts anti-reflecting layer, increase short reduction layer, thereby can strengthen bright dipping, the first luminescence unit comprises the first red light luminescent layer stacking gradually, green luminescence layer and the first blue light-emitting, and the material of the first blue light-emitting comprises the first Blue-light emitting host material and co-doped the first blue light guest materials and the first charge generating material in the first Blue-light emitting host material, the second luminescence unit comprises the second red light luminescent layer and is laminated in the second blue light-emitting on the second red light luminescent layer, make above-mentioned white light organic electroluminescent device there is higher luminous efficiency, luminous efficiency can reach 17.4lm/W, stacked structure can effectively reduce operating current, therefore, above-mentioned white light organic electroluminescent device has less operating current.
Accompanying drawing explanation
Fig. 1 is the structural representation of the white light organic electroluminescent device of an execution mode;
Fig. 2 is preparation method's the flow chart of the white light organic electroluminescent device of an execution mode.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments organic electroluminescence device and preparation method thereof is described in further detail below.
As shown in Figure 1, the organic electroluminescence device 100 of one execution mode, comprises the anode 101, the first hole injection layer 102, the first hole transmission layer 103, the first luminescence unit 104, the first electron transfer layer 105, charge generation layer 106, the second hole injection layer 107, the second hole transmission layer 108, the second luminescence unit 109, the second electron transfer layer 110, electron injecting layer 111 and the negative electrode 112 that stack gradually.
Anode 101 comprises the first anti-reflecting layer 1011, glass substrate 1012, the second anti-reflecting layer 1013, dioptric layer 1014, transparency conducting layer 1015, the first short reduction layer 1016 and the second short reduction layer 1017 stacking gradually.Glass substrate is preferably alkali-free glass.Alkali-free glass main component is SiO
2, Al
2o
3, CaO, MgO and B
2o
3, wherein alkali metal total content is less than one of percentage.The thickness of glass substrate 1012 is 0.3mm～0.7mm.
The first anti-reflecting layer 1011 and the second anti-reflecting layer 1013 sputter at respectively two surfaces of glass substrate 1012, preferably, the material of the first anti-reflecting layer 1011 and the second anti-reflecting layer 1013 is SiGe, preferably, the thickness of the first anti-reflecting layer 1011 and the second anti-reflecting layer 1013 is 10 nanometer～20 nanometers.
The material of dioptric layer 1014 is that refractive index is 1.7～1.9 transparent plastic, and preferred, the material of dioptric layer 1014 is polyurethane plastic (PU), PEN (PEN) or polyimides (PI).Dioptric layer 1014 has high refraction index, can strengthen bright dipping.Dioptric layer 1014 is formed with the projection of a plurality of spaced strips near the surface of the second anti-reflecting layer 1013, the cross section of projection is semicircle, projection end and the second anti-reflecting layer 1013 butts and be bonded together, make to form a plurality of spaces between dioptric layer 1014 and the second anti-reflecting layer 1013.Space can reach the effect that strengthens bright dipping.Further, the bearing of trend of a plurality of projections is parallel to each other, and a plurality of projection equidistantly arranges, and preferred, each protruding diameter is 5 microns～20 microns, and the distance between adjacent two projections is 5 microns～20 microns.In present embodiment, end and second anti-reflecting layer 1013 of projection are bonded together by index-matching fluid.
Transparency conducting layer 1015 is formed at dioptric layer 1014 away from a side surface of projection.The material of transparency conducting layer 1015 is the conventional transparent material with electric conductivity in this area, is preferably indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).The thickness of transparency conducting layer 1015 is 80nm～150nm.
On transparency conducting layer 1015, magnetron sputtering is prepared the first short reduction layer 1016 and the second short reduction layer 1017 successively, preferably, the material of the first short reduction layer 1016 is SiGe, the material of the second short reduction layer 1017 is selected from least one of indium oxide, zinc sulphide, tin oxide and silicon dioxide, preferably, the thickness of the first short reduction layer 1016 and the second short reduction layer 1017 is 2 nanometer～5 nanometers.
The first hole injection layer 102 is formed at the second short reduction layer 1017 surfaces.Wherein, the material of the first hole injection layer 102 comprises hole mobile material and is doped in the p-type dopant material in hole mobile material.The mass ratio of p-type dopant material and hole mobile material is 0.25～0.35:1.Hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane (TAPC).P-type dopant material is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2o
5) and rhenium trioxide (ReO
3) at least one.Preferably, the thickness of the first hole injection layer 102 is 10 nanometer～15 nanometers.
The first hole transmission layer 103 is formed at the first hole injection layer 102 surfaces.The material of the first hole transmission layer 103 is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane (TAPC).Preferably, the thickness of the first hole transmission layer 103 is 30 nanometer～50 nanometers.
The first luminescence unit 104 comprises the first red light luminescent layer 1041, green luminescence layer 1042 and the first blue light-emitting 1043 stacking gradually.
The first red light luminescent layer 1041 is formed at the first hole transmission layer 103 surfaces.The material of the first red light luminescent layer 1041 comprises the first ruddiness material of main part and is doped in the first ruddiness guest materials in the first ruddiness material of main part.The mass ratio of the first ruddiness guest materials and the first ruddiness material of main part is 0.005～0.02:1.Preferably, the first ruddiness material of main part is selected from 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in two (1-naphthyl) anthracenes (ADN) of cyclohexane (TAPC) and 9,10-.The first ruddiness guest materials is selected from two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) and closes iridium (Ir (MDQ)
2(acac)), two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi)
2ir (acac)), two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) closes iridium (III) ((F-BT)
2ir (acac)), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp)
2(acac)) and three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) at least one.Preferably, the thickness of the first red light luminescent layer 1041 is 10 nanometer～30 nanometers.
Green luminescence layer 1042 is formed at the first red light luminescent layer 1041 surfaces.The material of green luminescence layer 1042 comprises green glow material of main part and is doped in the green glow guest materials in green glow material of main part.The mass ratio of green glow guest materials and green glow material of main part is 0.02～0.1:1.Green glow material of main part is selected from 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in two (1-naphthyl) anthracenes (ADN) of cyclohexane (TAPC) and 9,10-.Green glow guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) and three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy)
3) at least one.Preferably, the thickness of green luminescence layer 1042 is 10 nanometer～30 nanometers.
The first blue light-emitting 1043 is formed at the surface of green luminescence layer 1042.The material of the first blue light-emitting 1043 comprises the first Blue-light emitting host material and co-doped the first blue light guest materials and the first charge generating material in the first Blue-light emitting host material.The mass ratio of the first blue light guest materials and the first Blue-light emitting host material is 0.05～0.2:1; The mass ratio of the first charge generating material and the first Blue-light emitting host material is 0.05～0.1:1.The first Blue-light emitting host material is selected from 4,4'-bis-(9-carbazole) biphenyl (CBP), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles (CzSi), 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY), 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine (35DCzPPY) and the Isosorbide-5-Nitraes of 5---at least one in two (triphenyl silicon) benzene (UGH2).The first blue light guest materials is selected from two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr), two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium (FIrtaz) and two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) and close at least one in iridium (FIrN4).The first charge generating material is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2o
5) and rhenium trioxide (ReO
3) at least one.Charge generating material belongs to bipolar materials, not only hole can be provided but also electronics can be provided.Preferably, the thickness of the first blue light-emitting 1043 is 5 nanometer～15 nanometers.
The first electron transfer layer 105 is formed at the first blue light-emitting 1043 surfaces.The material of the first electron transfer layer 105 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, at least one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).Preferably, the thickness of the first electron transfer layer 105 is 10 nanometer～60 nanometers.
Charge generation layer 106 is formed at the surface of the first electron transfer layer 105.The material of charge generation layer 106 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2o
5) and rhenium trioxide (ReO
3) at least one.These materials are ambipolar material, use the charge generation layer 106 of these materials also to have bipolarity.Preferably, the thickness of charge generation layer 106 is 5 nanometer～30 nanometers.
The second hole injection layer 107 is formed at the surface of charge generation layer 106.The material of the second hole injection layer 107 comprises hole mobile material and is doped in the p-type dopant material in hole mobile material.The mass ratio of p-type dopant material and hole mobile material is 0.25～0.35:1.Hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane (TAPC).P-type dopant material is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2o
5) and rhenium trioxide (ReO
3) at least one.The thickness of the second hole injection layer 107 is 10nm～15nm.
The second hole transmission layer 108 is formed at the surface of the second hole injection layer 107.The material of the second hole transmission layer 108 is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane (TAPC).The thickness of the second hole transmission layer 108 is 30nm～50nm.
The second luminescence unit 109 comprises the second red light luminescent layer 1091 and is laminated in the second blue light-emitting 1092 on the second red light luminescent layer 1091.
The second red light luminescent layer 1091 is formed at the second hole transmission layer 108 surfaces.The material of the second red light luminescent layer 1091 comprises the second ruddiness material of main part and is doped in the second ruddiness guest materials in the second ruddiness material of main part.The mass ratio of the second ruddiness guest materials and the second ruddiness material of main part is 0.005～0.02:1.The second ruddiness material of main part is selected from 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in two (1-naphthyl) anthracenes (ADN) of cyclohexane (TAPC) and 9,10-.The second ruddiness guest materials is that two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)), two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi)
2ir (acac)), two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) closes iridium (III) ((F-BT)
2ir (acac)), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp)
2(acac)) and three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) at least one.Preferably, the thickness of the second red light luminescent layer 1091 is 10 nanometer～30 nanometers.
The material of the second blue light-emitting 1092 comprises the second Blue-light emitting host material and co-doped the second blue light guest materials and the second charge generating material in the second Blue-light emitting host material.The mass ratio of the second blue light guest materials and the second Blue-light emitting host material is 0.05～0.2:1; The mass ratio of the second charge generating material and the second Blue-light emitting host material is 0.05～0.1:1.The second Blue-light emitting host material is selected from 4,4'-bis-(9-carbazole) biphenyl (CBP), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles (CzSi), 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY), 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine (35DCzPPY) and the Isosorbide-5-Nitraes of 5---at least one in two (triphenyl silicon) benzene (UGH2).The second blue light guest materials is selected from two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr), two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium (FIrtaz) and two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) and close at least one in iridium (FIrN4).The second charge generating material is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2o
5) and rhenium trioxide (ReO
3) at least one.Charge generating material belongs to bipolar materials, not only hole can be provided but also electronics can be provided.Preferably, the thickness of the second blue light-emitting 1092 is 5 nanometer～15 nanometers.
The second electron transfer layer 110 is formed at the second blue light-emitting 1092 surfaces.The material of the second electron transfer layer 110 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, at least one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).Preferably, the thickness of the second electron transfer layer 110 is 10 nanometer～60 nanometers.
The material of electron injecting layer 111 comprises electron transport material and is doped in the N-shaped dopant material in electron transport material.The mass ratio of N-shaped dopant material and electron transport material is 0.25～0.35:1.Electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 4, and 7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, at least one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).N-shaped dopant material is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), cesium azide (CsN
3), lithium carbonate (Li
2cO
3), lithium fluoride (LiF) and lithia (Li
2o) at least one in.Preferably, the thickness of electron injecting layer 111 is 20 nanometer～40 nanometers.
The material of negative electrode 112 is at least one in silver (Ag), aluminium (Al) and gold (Au).Preferably, the thickness of negative electrode 115 is 50 nanometer～200 nanometers.
Above-mentioned white light organic electroluminescent device 100 comprises the anode 101 stacking gradually, the first hole injection layer 102, the first hole transmission layer 103, the first luminescence unit 104, the first electron transfer layer 105, charge generation layer 106, the second hole injection layer 107, the second hole transmission layer 108, the second luminescence unit 109, the second electron transfer layer 110, electron injecting layer 111 and negative electrode 112, employing be PIN laminated construction, and anode 101 comprises the first anti-reflecting layer 1011 stacking gradually, glass substrate 1012, the second anti-reflecting layer 1013, dioptric layer 1014, transparency conducting layer 1015, the first short reduction layer 1016 and the second short reduction layer 1017, the surface that dioptric layer 1014 is relative with the second anti-reflecting layer 1013 is provided with the projection of a plurality of spaced strips, the cross section of projection is semicircle, projection end and the second anti-reflecting layer butt and be bonded together, make to form a plurality of spaces between dioptric layer 1014 and the second anti-reflecting layer 1013, described transparency conducting layer 1015 is laminated in described dioptric layer 1014 away from a side of described projection, the material of the first short reduction layer 1016 is SiGe, and the material of the second short reduction layer 1017 is selected from indium oxide, zinc sulphide, at least one of tin oxide and silicon dioxide, by new bright dipping mode, adopts anti-reflecting layer, increases short reduction layer, thereby can strengthen bright dipping, the first luminescence unit 104 comprises the first red light luminescent layer 1041 stacking gradually, green luminescence layer 1042 and the first blue light-emitting 1043, and the material of the first blue light-emitting 1042 comprises the first Blue-light emitting host material and co-doped the first blue light guest materials and the first charge generating material in the first Blue-light emitting host material, the second luminescence unit 109 comprises the second red light luminescent layer 1091 and is laminated in the second blue light-emitting 1092 on the second red light luminescent layer 1091, whole white light organic electroluminescent device device spectral coverage is wide, half-wave peak width, color rendering index is high like this, between the first luminescence unit 104 and the second luminescence unit 109, charge generation layer 106 is set, make above-mentioned white light organic electroluminescent device 100 there is higher luminous efficiency, luminous efficiency can reach 17.4lm/W, stacked structure can effectively reduce operating current under equal brightness, therefore, above-mentioned white light organic electroluminescent device 100 has less operating current.
As shown in Figure 2, the preparation method of the white light organic electroluminescent device of an execution mode, comprises the steps:
Step S310, on glass substrate 1012 two sides, the first anti-reflecting layer 1011 and the second anti-reflecting layer 1013 are prepared in sputter respectively.
Glass substrate 1012 is preferably alkali-free glass.Alkali-free glass main component is SiO
2, Al
2o
3, CaO, MgO and B
2o
3, wherein alkali metal total content is less than one of percentage.The thickness of glass substrate 1012 is 0.3mm～0.7mm.
The first anti-reflecting layer and the second anti-reflecting layer adopt sputter to make, and preferred, the material of the first anti-reflecting layer and the second anti-reflecting layer is SiGe, and the thickness of the first anti-reflecting layer and the second anti-reflecting layer is 10 nanometer～20 nanometers.
Step S320, dioptric layer 1014 is pressed on the second anti-reflecting layer 1013 of glass substrate 1012, dioptric layer 1014 is formed with the projection of a plurality of spaced strips near the surface of the second anti-reflecting layer 1013, the cross section of projection be semicircle, protruding end and the second anti-reflecting layer 1013 butts and being bonded together.
Specifically in the present embodiment, by the end protruding, applying a small amount of index-matching fluid makes protruding end and described the second anti-reflecting layer butt and is bonded together.
Preferably, dioptric layer is pressed into and also comprises before the second anti-reflecting layer one side surface glass substrate is cleaned and the step of surface activation process successively; The step of cleaning is: glass substrate is adopted to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, and then dry.In specific embodiment, clean 5 minutes at every turn, stop 5 minutes, repeat respectively 3 times, and then use oven for drying.By the glass substrate to after cleaning, carry out surface activation process, can increase the oxygen content of glass baseplate surface, improve the work function of glass baseplate surface.
The transparent plastic that the material of dioptric layer 1014 is 1.7～1.9 for refractive index, preferred, the material of dioptric layer 1014 is polyurethane plastic (PU), PEN (PEN) or polyimides (PI).Dioptric layer 1014 has high refraction index, can strengthen bright dipping.On the surface of dioptric layer 1014 near the second anti-reflecting layer 1013, be formed with the projection of a plurality of spaced strips, the cross section of projection is semicircle, projection end and the second anti-reflecting layer 1013 butts and be bonded together, make to form a plurality of spaces between dioptric layer 1014 and the second anti-reflecting layer 1013.Space can reach the effect that strengthens bright dipping.Further, the bearing of trend of a plurality of projections is parallel to each other, and a plurality of projection equidistantly arranges, and preferred, each protruding diameter is 5 microns～20 microns, and the distance between adjacent two projections is 5 microns～20 microns.
In present embodiment, the operation that dioptric layer 1014 is pressed into the second anti-reflecting layer 1,013 one side surfaces comprises the following steps: at side surface coating one deck plastics glue of the second anti-reflecting layer 1013, thickness is about 30nm, then dioptric layer 1014 is molded on the second anti-reflecting layer 1013.By plastics glue, dioptric layer 1014 and the second anti-reflecting layer 1013 are bonded together, due to the thickness of plastics glue, compare the thickness of dioptric layer 1014 and the second anti-reflecting layer 1013 and can ignore, so plastics glue can exert an influence to light efficiency.
Step S330, the side surface deposit transparent conductive layer 1015 at dioptric layer 1014 away from projection.
Transparency conducting layer 1015 is formed at dioptric layer 1014 away from a side surface of projection.The material of transparency conducting layer 1015 is the conventional transparent material with electric conductivity in this area, is preferably indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).The thickness of transparency conducting layer 1015 is 80nm～150nm.
Transparency conducting layer 1015 is prepared by sputter.During sputter, base vacuum degree 1 * 10
-5pa～1 * 10
-3pa, target is corresponding oxide, 300～800V, magnetic field approximately: 50～200G, power density: 1～40W/cm
2.
Step S340, on transparency conducting layer 1015, magnetron sputtering is prepared the first short reduction layer 1016 and the second short reduction layer 1017, the first anti-reflecting layers 1011, glass substrate 1012, the second anti-reflecting layer 1013, dioptric layer 1014, transparency conducting layer 1015, the first short reduction layer 1016 and the second short reduction layer 1017 and is formed anodes 101 successively.
The first short reduction layer 1016 and the second short reduction layer 1017 are formed at a side surface of transparency conducting layer 1015.The material of the first short reduction layer 1016 is SiGe, 1017 materials of the second short reduction layer are selected from least one of indium oxide, zinc sulphide, tin oxide and silicon dioxide, and the thickness of the first short reduction layer 1016 and the second short reduction layer 1017 is 2 nanometer～5 nanometers.
In present embodiment, the first short reduction layer 1016 and the second short reduction layer 1017 all adopt the mode of magnetron sputtering to make.During sputter, base vacuum degree is 1 * 10
-3～1 * 10
-5pa.Preferably, before vacuum evaporation forms the first hole injection layer on the second short reduction layer, also comprise anode 101 in 60 ℃～80 ℃ vacuumizes 15～30 minutes, thereby reduce remaining water and gas.
Step S350, on the second short reduction layer 1017 surfaces successively evaporation, prepare the first hole injection layer 102 and the first hole transmission layer 103.
The first hole injection layer 102 is formed at the second short reduction layer 1017 surfaces.Wherein, the material of the first hole injection layer 102 comprises hole mobile material and is doped in the p-type dopant material in hole mobile material.The mass ratio of p-type dopant material and hole mobile material is 0.25～0.35:1.Hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane (TAPC).P-type dopant material is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2o
5) and rhenium trioxide (ReO
3) at least one.Preferably, the thickness of the first hole injection layer 102 is 10 nanometer～15 nanometers.Preferably, to form the vacuum degree of the first hole injection layer 102 be 8 * 10 in vacuum evaporation
-5pa～3 * 10
-4pa, the evaporation rate of p-type dopant material is
The first hole transmission layer 103 is formed at the first hole injection layer 102 surfaces.The material of the first hole transmission layer 103 is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane (TAPC).Preferably, the thickness of the first hole transmission layer 130 is 30 nanometer～50 nanometers.Preferably, to form the vacuum degree of the first hole transmission layer 103 be 8 * 10 in vacuum evaporation
-5pa～3 * 10
-4pa, evaporation rate is
Step S360, at the surperficial evaporation of the first hole transmission layer 103, prepare the first luminescence unit 104.
The first luminescence unit 104 comprises the first red light luminescent layer 1041, green luminescence layer 1042 and the first blue light-emitting 1043 stacking gradually.
The first red light luminescent layer 1041 is formed at the first hole transmission layer 103 surfaces.The material of the first red light luminescent layer 1041 comprises the first ruddiness material of main part and is doped in the first ruddiness guest materials in the first ruddiness material of main part.The mass ratio of the first ruddiness guest materials and the first ruddiness material of main part is 0.005～0.02:1.Preferably, the first ruddiness material of main part is selected from 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in two (1-naphthyl) anthracenes (ADN) of cyclohexane (TAPC) and 9,10-.The first ruddiness guest materials is selected from two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) and closes iridium (Ir (MDQ)
2(acac)), two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi)
2ir (acac)), two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) closes iridium (III) ((F-BT)
2ir (acac)), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp)
2(acac)) and three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) at least one.Preferably, the thickness of the first red light luminescent layer 1041 is 10 nanometer～30 nanometers.Preferably, to form the vacuum degree of the first red light luminescent layer be 8 * 10 in vacuum evaporation
-5pa～3 * 10
-4pa, adopts mixed mode of steaming, and after preparing by the setting mass ratio of the first ruddiness material of main part and the first ruddiness guest materials, puts into a crucible, and evaporation rate is
Green luminescence layer 1042 is formed at the first red light luminescent layer 1041 surfaces.The material of green luminescence layer 1042 comprises green glow material of main part and is doped in the green glow guest materials in green glow material of main part.The mass ratio of green glow guest materials and green glow material of main part is 0.02～0.1:1.Green glow material of main part is selected from 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in two (1-naphthyl) anthracenes (ADN) of cyclohexane (TAPC) and 9,10-.Green glow guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) and three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy)
3) at least one.Preferably, the thickness of green luminescence layer 1042 is 10 nanometer～30 nanometers.Preferably, the vacuum degree of vacuum evaporation formation green luminescence layer is 8 * 10
-5pa～3 * 10
-4pa, adopts mixed mode of steaming, and after the mass ratio of setting by green glow material of main part and green glow guest materials prepares, puts into a crucible, and evaporation rate is
The first blue light-emitting 1043 is formed at the surface of green light emitting layer 1042.The material of the first blue light-emitting 1043 comprises the first Blue-light emitting host material and co-doped the first blue light guest materials and the first charge generating material in the first Blue-light emitting host material.The mass ratio of the first blue light guest materials and the first Blue-light emitting host material is 0.05～0.2:1; The mass ratio of the first charge generating material and the first Blue-light emitting host material is 0.05～0.1:1.The first Blue-light emitting host material is selected from 4,4'-bis-(9-carbazole) biphenyl (CBP), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles (CzSi), 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY), 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine (35DCzPPY) and the Isosorbide-5-Nitraes of 5---at least one in two (triphenyl silicon) benzene (UGH2).The first blue light guest materials is selected from two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr), two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium (FIrtaz) and two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) and close at least one in iridium (FIrN4).The first charge generating material is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2o
5) and rhenium trioxide (ReO
3) at least one.Preferably, the thickness of the first blue light-emitting 1043 is 5 nanometer～15 nanometers.Preferably, to form the vacuum degree of the first blue light-emitting be 8 * 10 in vacuum evaporation
-5pa～3 * 10
-4pa, adopts mixed mode of steaming, and after preparing by the mass ratio of the setting of the first Blue-light emitting host material, the first blue light guest materials and the first charge generating material, puts into a crucible, and evaporation rate is
Step S370, at the surperficial evaporation of the first blue light-emitting 1043, prepare the first electron transfer layer 105.
The first electron transfer layer 105 is formed at the first blue light-emitting 1043 surfaces.The material of the first electron transfer layer 105 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, at least one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).Preferably, the thickness of the first electron transfer layer 105 is 10 nanometer～60 nanometers.Preferably, to form the vacuum degree of the first electron transfer layer be 8 * 10 in vacuum evaporation
-5pa～3 * 10
-4pa, evaporation rate is
Step S380, at the surperficial evaporation of the first electron transfer layer 105, prepare charge generation layer 106.
Charge generation layer 106 is formed at the surface of the first electron transfer layer 105.The material of charge generation layer 106 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2o
5) and rhenium trioxide (ReO
3) at least one.These materials are ambipolar material, use the charge generation layer 108 of these materials also to have bipolarity.Preferably, the thickness of charge generation layer 106 is 5 nanometer～30 nanometers.Preferably, the vacuum degree of vacuum evaporation formation charge generation layer is 8 * 10
-5pa～3 * 10
-4pa, evaporation rate is
Step S390, at the surperficial evaporation of charge generation layer 106, prepare the second hole injection layer 107 and the second hole transmission layer 108.
The second hole injection layer 107 is formed at the surface of charge generation layer 106.The material of the second hole injection layer 107 comprises hole mobile material and is doped in the p-type dopant material in hole mobile material.The mass ratio of p-type dopant material and hole mobile material is 0.25～0.35:1.Hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane (TAPC).P-type dopant material is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2o
5) and rhenium trioxide (ReO
3) at least one.The thickness of the second hole injection layer 107 is 10nm～15nm.Preferably, to form the vacuum degree of the second hole injection layer be 8 * 10 in vacuum evaporation
-5pa～3 * 10
-4pa, p-type dopant material evaporation rate is
The second hole transmission layer 108 is formed at the surface of the second hole injection layer 107.The material of the second hole transmission layer 108 is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane (TAPC).The thickness of the second hole transmission layer 108 is 30nm～50nm.Preferably, to form the vacuum degree of the second hole transmission layer be 8 * 10 in vacuum evaporation
-5pa～3 * 10
-4pa, evaporation rate is
Step S400, on the second hole transmission layer 108 vacuum evaporation the second luminescence unit 109.
The second luminescence unit 109 comprises the second red light luminescent layer 1091 and is laminated in the second blue light-emitting 1092 on the second red light luminescent layer 1091.
The second red light luminescent layer 1091 is formed at the second hole transmission layer 108 surfaces.The material of the second red light luminescent layer 1091 comprises the second ruddiness material of main part and is doped in the second ruddiness guest materials in the second ruddiness material of main part.The mass ratio of the second ruddiness guest materials and the second ruddiness material of main part is 0.005～0.02:1.The second ruddiness material of main part is selected from 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in two (1-naphthyl) anthracenes (ADN) of cyclohexane (TAPC) and 9,10-.The second ruddiness guest materials is that two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)), two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi)
2ir (acac)), two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) closes iridium (III) ((F-BT)
2ir (acac)), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp)
2(acac)) and three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) at least one.Preferably, the thickness of the second red light luminescent layer 1091 is 10 nanometer～30 nanometers.Preferably, to form the vacuum degree of described the second red light luminescent layer be 8 * 10 in vacuum evaporation
-5pa～3 * 10
-4pa, adopts mixed mode of steaming, and after the mass ratio of setting by the second ruddiness material of main part and the second ruddiness guest materials prepares, puts into a crucible, and evaporation rate is
The material of the second blue light-emitting 1092 comprises the second Blue-light emitting host material and co-doped the second blue light guest materials and the second charge generating material in the second Blue-light emitting host material.The mass ratio of the second blue light guest materials and the second Blue-light emitting host material is 0.05～0.2:1; The mass ratio of the second charge generating material and the second Blue-light emitting host material is 0.05～0.1:1.The second Blue-light emitting host material is selected from 4,4'-bis-(9-carbazole) biphenyl (CBP), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles (CzSi), 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY), 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine (35DCzPPY) and the Isosorbide-5-Nitraes of 5---at least one in two (triphenyl silicon) benzene (UGH2).The second blue light guest materials is selected from two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr), two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium (FIrtaz) and two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) and close at least one in iridium (FIrN4).The second charge generating material is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2o
5) and rhenium trioxide (ReO
3) at least one.Preferably, the thickness of the second blue light-emitting 1092 is 5 nanometer～15 nanometers.Preferably, to form the vacuum degree of described the second blue light-emitting be 8 * 10 in vacuum evaporation
-5pa～3 * 10
-4pa, adopts mixed mode of steaming, and after the mass ratio of setting by the second Blue-light emitting host material, the second blue light guest materials and the second charge generating material prepares, puts into a crucible, and evaporation rate is
Step S410, on the second blue light-emitting 1092, evaporation is prepared the second electron transfer layer 110, electron injecting layer 111 and negative electrode 112 successively, obtains white light organic electroluminescent device.
The second electron transfer layer 110 is formed at the second blue light-emitting 1092 surfaces.The material of the second electron transfer layer 110 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, at least one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).Preferably, the thickness of the second electron transfer layer 110 is 10 nanometer～60 nanometers.Preferably, to form the vacuum degree of the second electron transfer layer be 8 * 10 in vacuum evaporation
-5pa～3 * 10
-4pa, evaporation rate is
The material of electron injecting layer 111 comprises electron transport material and is doped in the N-shaped dopant material in electron transport material.The mass ratio of N-shaped dopant material and electron transport material is 0.25～0.35:1.Electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 4, and 7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, at least one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).N-shaped dopant material is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), cesium azide (CsN
3), lithium carbonate (Li
2cO
3), lithium fluoride (LiF) and lithia (Li
2o) at least one in.Preferably, the thickness of electron injecting layer 111 is 20 nanometer～40 nanometers.Preferably, the vacuum degree of vacuum evaporation formation electron injecting layer is 8 * 10
-5pa～3 * 10
-4pa, N-shaped dopant material evaporation rate is
The material of negative electrode 112 is at least one in silver (Ag), aluminium (Al) and gold (Au).Preferably, the thickness of negative electrode 112 is 50 nanometer～200 nanometers.Preferably, the vacuum degree of vacuum evaporation formation negative electrode is 8 * 10
-5pa～3 * 10
-4pa, evaporation rate is
The preparation method of above-mentioned white light organic electroluminescent device is simple, and easily operation, and the organic electroluminescence device of preparing has higher color rendering index and less operating current, is conducive to industrialization and produces.
Below in conjunction with specific embodiment, the preparation method of flexible white light organic electroluminescence device provided by the invention is elaborated.
The preparation used of the embodiment of the present invention and comparative example and tester are: high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics are, CS-100A colorimeter test brightness and the colourity of the Keithley2400 of U.S. Keithley company test electric property, Japanese Konica Minolta company.
Embodiment 1
The structure of the white light organic electroluminescent device of the present embodiment is: SiGe/ glass/SiGe/PU/ITO/SiGe/In
2o
3/ NPB:MoO
3/ NPB/TCTA:Ir (MDQ)
2(acac)/TCTA:Ir (ppy)
3/ CBP:Firpic:MoO
3/ Bphen/MoO
3/ NPB:MoO
3/ NPB/TCTA:Ir (MDQ)
2(acac)/CBP:Firpic:MoO
3/ Bphen/Bphen:Cs
2cO
3/ Ag; Wherein, brace "/" represents layer structure, and colon ": " represents doping, lower same.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) glass substrate that is 0.5mm by thickness adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On glass substrate two sides, the first anti-reflecting layer and the second anti-reflecting layer are prepared in sputter respectively, and film material is SiGe, and the thickness of the first anti-reflecting layer and the second anti-reflecting layer is 20 nanometers; Choose there is high refractive index transparent polyurethane film as dioptric layer, one surface of dioptric layer is formed with the projection of a plurality of spaced strips, the cross section of projection is semicircle, and each protruding diameter is 5 microns, and the distance between adjacent two projections is 5 microns; Dioptric layer is formed with to protruding surface and the second anti-reflecting layer pressing, between dioptric layer and the second anti-reflecting layer, forms a plurality of spaces; Then at dioptric layer, away from a side surface deposition of hemispherical projections, form indium tin oxide (ITO) transparency conducting layer, the thickness of transparency conducting layer is 100nm; Adopt the mode of magnetron sputtering on transparency conducting layer, to prepare successively the first short reduction layer and the second short reduction layer, the material of the first short reduction layer is SiGe, the material of the second short reduction layer is indium oxide, the thickness of the first short reduction layer and the second short reduction layer is 5 nanometers, obtain anode, by anode in 80 ℃ of vacuumizes 15 minutes; The structure of anode is: SiGe/ glass/SiGe/PU/ITO/SiGe/In
2o
3.
(2) on the second short reduction layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is molybdenum trioxide (MoO
3) doping N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), is expressed as: NPB:MoO
3, wherein, molybdenum trioxide (MoO
3) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) mass ratio is 0.3:1, and the thickness of the first hole injection layer is 12.5 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, MoO
3evaporation rate is
the material of the first hole transmission layer is N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(3) vacuum evaporation the first luminescence unit on the first hole transmission layer, the first luminescence unit comprises the first red light luminescent layer, green luminescence layer and the first blue light-emitting, on the first hole transmission layer, vacuum evaporation forms the first red light luminescent layer, green luminescence layer and the first blue light-emitting successively: the material of the first red light luminescent layer is that two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)) 4 of doping, 4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:Ir (MDQ)
2(acac), wherein, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)) with 4,4', the mass ratio of 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) is 0.01:1, and the thickness of the first red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of green luminescence layer is that three (2-phenylpyridines) close iridium (Ir (ppy)
3) doping 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:Ir (ppy)
3, wherein, three (2-phenylpyridines) close iridium (Ir (ppy)
3) with 4,4', the mass ratio of 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) is 0.06:1, and the thickness of green luminescence layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the first blue light-emitting is that two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls close iridium (FIrpic) and molybdenum trioxide (MoO
3) co-doped 4,4'-bis-(9-carbazole) biphenyl (CBP), is expressed as CBP:FIrpic:MoO
3, wherein, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic) and 4, and the mass ratio of 4'-bis-(9-carbazole) biphenyl (CBP) is 0.125:1, molybdenum trioxide (MoO
3) with 4, the mass ratio of 4'-bis-(9-carbazole) biphenyl (CBP) is 0.075:1, the thickness of the first blue light-emitting is 10 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the first luminescence unit is expressed as: TCTA:Ir (MDQ)
2(acac)/TCTA:Ir (ppy)
3/ CBP:FIrpic:MoO
3.
(4) on the first blue light-emitting, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer: the material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), thickness is 35 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of charge generation layer is molybdenum trioxide (MoO
3), thickness is 17.5 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole injection layer is molybdenum trioxide (MoO
3) doping N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), is expressed as: NPB:MoO
3, wherein, molybdenum trioxide (MoO
3) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the mass ratio of 4'-diamines (NPB) is 0.3:1, and the thickness of the second hole injection layer is 12.5 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole transmission layer is N, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(5) vacuum evaporation the second luminescence unit on the second hole transmission layer, the second luminescence unit comprises the second red light luminescent layer and the second blue light-emitting, on the second hole transmission layer, vacuum evaporation forms the second red light luminescent layer and the second blue light-emitting successively: the material of the second red light luminescent layer is that two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)) 4 of doping, 4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:Ir (MDQ)
2) (acac), wherein, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)) with 4,4', the mass ratio of 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) is 0.01:1, and the thickness of the second red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second blue light-emitting is that two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls close iridium (FIrpic) and molybdenum trioxide (MoO
3) co-doped 4,4'-bis-(9-carbazole) biphenyl (CBP), is expressed as CBP:FIrpic:MoO
3, wherein, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic) and 4, and the mass ratio of 4'-bis-(9-carbazole) biphenyl (CBP) is 0.125:1, molybdenum trioxide (MoO
3) with 4, the mass ratio of 4'-bis-(9-carbazole) biphenyl (CBP) is 0.075:1, the thickness of the second blue light-emitting is 10 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the second luminescence unit is expressed as: TCTA:Ir (MDQ)
2(acac)/CBP:Firpic:MoO
3.
(6) on the second blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and negative electrode successively, obtain white light organic electroluminescent device: the material of the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), thickness is 35 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of electron injecting layer is cesium carbonate (Cs
2cO
3) doping 4,7-diphenyl-1,10-phenanthroline (Bphen), is expressed as: Bphen:Cs
2cO
3, wherein, cesium carbonate (Cs
2cO
3) with 4,7-diphenyl-1,10-phenanthroline (Bphen) mass ratio is 0.3:1, and the thickness of electron injecting layer is 30 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, Cs
2cO
3evaporation rate is
the material of negative electrode is silver (Ag), and thickness is 125 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
The structure that obtains the present embodiment is SiGe/ glass/SiGe/PU/ITO/SiGe/In
2o
3/ NPB:MoO
3/ NPB/TCTA:Ir (MDQ)
2(acac)/TCTA:Ir (ppy)
3/ CBP:FIrpic:MoO
3/ Bphen/MoO
3/ NPB:MoO
3/ NPB/TCTA:Ir (MDQ)
2(acac)/CBP:FIrpic:MoO
3/ Bphen/Bphen:Cs
2cO
3the white light organic electroluminescent device of/Ag.The luminous efficiency of white light organic electroluminescent device prepared by the present embodiment is in Table 1.
Embodiment 2
The structure of the white light organic electroluminescent device of the present embodiment is: SiGe/ glass SiGe/PEN/ITO/SiGe/ZnS/TCTA:WO
3/ TCTA/mCP:PQIr/mCP:Ir (ppy)
2(acac)/mCP:FIr6:V
2o
5/ BCP/V
2o
5/ TCTA:WO
3/ TCTA/mCP:PQIr/mCP:FIr6:V
2o
5/ BCP/BCP:CsF/Al.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) glass substrate that is 0.3mm by thickness adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On glass substrate two sides, the first anti-reflecting layer and the second anti-reflecting layer are prepared in sputter respectively, and film material is SiGe, and the thickness of the first anti-reflecting layer and the second anti-reflecting layer is 20 nanometers; Choose there is high refractive index transparent PEN (PEN) as dioptric layer, one surface of dioptric layer is formed with the projection of a plurality of spaced strips, the cross section of projection is semicircle, each protruding diameter is 10 microns, and the distance between adjacent two projections is 10 microns; Dioptric layer is formed with to protruding surface and the second anti-reflecting layer pressing, between dioptric layer and the second anti-reflecting layer, forms a plurality of spaces; Then at dioptric layer, away from a side surface deposition of hemispherical projections, form ITO transparency conducting layer, the thickness of transparency conducting layer is 150nm; Adopt the mode of magnetron sputtering on transparency conducting layer, to prepare successively the first short reduction layer and the second short reduction layer, the material of the first short reduction layer is SiGe, the material of the second short reduction layer is zinc sulphide, the thickness of the first short reduction layer and the second short reduction layer is 5 nanometers, obtain anode, by anode in 80 ℃ of vacuumizes 15 minutes; The structure of anode is: SiGe/ glass/SiGe/PEN/ITO/SiGe/ZnS.
(2) on the second short reduction layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is tungstic acid (WO
3) doping 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:WO
3, wherein, tungstic acid (WO
3) with 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) mass ratio is 0.25:1, and the thickness of the first hole injection layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, WO
3evaporation rate is
the material of the first hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), and thickness is 30 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(3) vacuum evaporation the first luminescence unit on the first hole transmission layer, the first luminescence unit comprises the first red light luminescent layer, green luminescence layer and the first blue light-emitting, on the first hole transmission layer, vacuum evaporation forms the first red light luminescent layer successively, green luminescence layer and the first blue light-emitting: the material of the first red light luminescent layer be two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close that iridium (III) (PQIr) adulterates 9, 9'-(1, 3-phenyl) two-9H-carbazole (mCP), be expressed as: mCP:PQIr, wherein, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr) with 9, 9'-(1, 3-phenyl) mass ratio of two-9H-carbazole (mCP) is 0.005:1, the thickness of the first red light luminescent layer is 10 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of green luminescence layer is acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) 9 of doping, 9'-(1,3-phenyl) two-9H-carbazole (mCP), is expressed as: mCP:Ir (ppy)
2(acac), wherein, acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)), with 9, the mass ratio of 9'-(1,3-phenyl) two-9H-carbazole (mCP) is 0.02:1, and the thickness of green luminescence layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the first blue light-emitting is that two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6) and vanadic oxide (V
2o
5) co-doped 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), is expressed as mCP:FIr6:V
2o
5, wherein, two (4,6-difluorophenyl pyridines)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6) and 9, and the mass ratio of 9'-(1,3-phenyl) two-9H-carbazole (mCP) is 0.05:1, vanadic oxide (V
2o
5) with 9, the mass ratio of 9'-(1,3-phenyl) two-9H-carbazole (mCP) is 0.05:1, the thickness of the first blue light-emitting is 5 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the first luminescence unit is expressed as: mCP:PQIr/mCP:Ir (ppy)
2(acac)/mCP:FIr6:V
2o
5.
(4) on the first blue light-emitting, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer: the material of the first electron transfer layer is 4,7-diphenyl-1,10-Phen (BCP), thickness is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of charge generation layer is vanadic oxide (V
2o
5), thickness is 5 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole injection layer is tungstic acid (WO
3) doping 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:WO
3, wherein, tungstic acid (WO
3) with 4,4', the mass ratio of 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) is 0.25:1, and the thickness of the second hole injection layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), and thickness is 30 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(5) vacuum evaporation the second luminescence unit on the second hole transmission layer, the second luminescence unit comprises the second red light luminescent layer and the second blue light-emitting, on the second hole transmission layer, vacuum evaporation forms the second red light luminescent layer and the second blue light-emitting successively: the material of the second red light luminescent layer be two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close that iridium (III) (PQIr) adulterates 9, 9'-(1, 3-phenyl) two-9H-carbazole (mCP), be expressed as: mCP:PQIr, wherein, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr) with 9, 9'-(1, 3-phenyl) mass ratio of two-9H-carbazole (mCP) is 0.005:1, the thickness of the second red light luminescent layer is 10 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second blue light-emitting is that two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6) and vanadic oxide (V
2o
5) co-doped 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), is expressed as mCP:FIr6:V
2o
5, wherein, two (4,6-difluorophenyl pyridines)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6) and 9, and the mass ratio of 9'-(1,3-phenyl) two-9H-carbazole (mCP) is 0.05:1, vanadic oxide (V
2o
5) with 9, the mass ratio of 9'-(1,3-phenyl) two-9H-carbazole (mCP) is 0.05:1, the thickness of the second blue light-emitting is 5 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the second luminescence unit is expressed as: mCP:PQIr/mCP:FIr6:V
2o
5.
(6) on the second blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and negative electrode successively, obtain organic electroluminescence device: the material of the second electron transfer layer is 4,7-diphenyl-1,10-Phen (BCP), thickness is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of electron injecting layer is 4 of cesium fluoride (CsF) doping, 7-diphenyl-1,10-Phen (BCP), be expressed as: BCP:CsF, wherein, cesium fluoride (CsF) and 4,7-diphenyl-1,10-Phen (BCP) mass ratio is 0.25:1, and the thickness of electron injecting layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, CsF evaporation rate is
the material of negative electrode is aluminium (Al), and thickness is 50 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
The structure that obtains the present embodiment is SiGe/ glass/SiGe/PEN/ITO/SiGe/ZnS/TCTA:WO
3/ TCTA/mCP:PQIr/mCP:Ir (ppy)
2(acac)/mCP:FIr6:V
2o
5/ BCP/V
2o
5/ TCTA:WO
3/ TCTA/mCP:PQIr/mCP:FIr6:V
2o
5the white light organic electroluminescent device of/BCP/BCP:CsF/Al.The luminous efficiency that has white light organic electroluminescence devices prepared by the present embodiment is in Table 1.
Embodiment 3
The structure of the white light organic electroluminescent device of the present embodiment is: SiGe/ glass/SiGe/PI/ITO/SiGe/SnO
2/ CBP:V
2o
5/ CBP/CBP:(fbi)
2ir (acac)/CBP:Ir (mppy)
3/ CzSi:FCNIr:WO
3/ BAlq/WO
3/ CBP:V
2o
5/ CBP/CBP:(fbi)
2ir (acac)/CzSi:FCNIr:WO
3/ BAlq/BAlq:CsN
3/ Au.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) glass substrate that is 0.7mm by thickness adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On glass substrate two sides, the first anti-reflecting layer and the second anti-reflecting layer are prepared in sputter respectively, and film material is SiGe, and the thickness of the first anti-reflecting layer and the second anti-reflecting layer is 20 nanometers; Choose there is high refractive index transparent polyimides (PI) as dioptric layer, one surface of dioptric layer is formed with the projection of a plurality of spaced strips, the cross section of projection is semicircle, and each protruding diameter is 15 microns, and the distance between adjacent two projections is 15 microns; Dioptric layer is formed with to protruding surface and the second anti-reflecting layer pressing, between dioptric layer and the second anti-reflecting layer, forms a plurality of spaces; Then at dioptric layer, away from a side surface deposition of hemispherical projections, form ITO transparency conducting layer, the thickness of transparency conducting layer is 80nm; Adopt the mode of magnetron sputtering on transparency conducting layer, to prepare successively the first short reduction layer and the second short reduction layer, the material of the first short reduction layer is SiGe, the material of the second short reduction layer is tin oxide, the thickness of the first short reduction layer and the second short reduction layer is 5 nanometers, obtain anode, by anode in 80 ℃ of vacuumizes 15 minutes; The structure of anode is: SiGe/ glass/SiGe/PI/ITO/SiGe/SnO
2.
(2) on the second short reduction layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is vanadic oxide (V
2o
5) doping 4,4'-bis-(9-carbazole) biphenyl (CBP), is expressed as: CBP:V
2o
5, wherein, vanadic oxide (V
2o
5) with 4,4'-bis-(9-carbazole) biphenyl (CBP) mass ratio is 0.35:1, the thickness of the first hole injection layer is 15 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, V
2o
5evaporation rate is
the material of the first hole transmission layer is 4,4'-bis-(9-carbazole) biphenyl (CBP), and thickness is 50 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(3) vacuum evaporation the first luminescence unit on the first hole transmission layer, the first luminescence unit comprises the first red light luminescent layer, green luminescence layer and the first blue light-emitting, and the material of the first red light luminescent layer is that two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi)
2ir (acac)) 4 of doping, 4'-bis-(9-carbazole) biphenyl (CBP), is expressed as: CBP:(fbi)
2ir (acac), wherein, two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi)
2ir (acac)) with 4, the mass ratio of 4'-bis-(9-carbazole) biphenyl (CBP) is 0.02:1, and the thickness of red light luminescent layer is 30 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of green luminescence layer is that three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy)
3) doping 4,4'-bis-(9-carbazole) biphenyl (CBP), is expressed as: CBP:Ir (mppy)
3, wherein, three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy)
3) with 4, the mass ratio of 4'-bis-(9-carbazole) biphenyl (CBP) is 0.1:1, the thickness of the first green luminescence layer is 30 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the first blue light-emitting is three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr) and tungstic acid (WO
3) 9-(4-2-methyl-2-phenylpropane base)-3 of co-doped, two (triphenyl the silicon)-9H-carbazoles (CzSi) of 6-, are expressed as CzSi:FCNIr:WO
3, wherein, three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr) and 9-(4-2-methyl-2-phenylpropane base)-3, the mass ratio of two (triphenyl the silicon)-9H-carbazoles (CzSi) of 6-is 0.2:1, tungstic acid (WO
3) and 9-(4-2-methyl-2-phenylpropane base)-3, the mass ratio of two (triphenyl the silicon)-9H-carbazoles (CzSi) of 6-is 0.1:1, and the thickness of the first blue light-emitting is 15 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the first luminescence unit is expressed as: CBP:(fbi)
2ir (acac)/CBP:Ir (mppy)
3/ CzSi:FCNIr:WO
3.
(4) vacuum evaporation the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer on the first blue light-emitting: the material of the first electron transfer layer is that 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), thickness is 60 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of charge generation layer is tungstic acid (WO
3), thickness is 30 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole injection layer is vanadic oxide (V
2o
5) doping 4,4'-bis-(9-carbazole) biphenyl (CBP), is expressed as: CBP:V
2o
5, wherein, vanadic oxide (V
2o
5) with 4, the mass ratio of 4'-bis-(9-carbazole) biphenyl (CBP) is 0.35:1, the thickness of the second hole injection layer is 15 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole transmission layer is 4,4'-bis-(9-carbazole) biphenyl (CBP), and thickness is 50 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(5) vacuum evaporation the second luminescence unit on the second hole transmission layer, the second luminescence unit comprises the second red light luminescent layer and the second blue light-emitting, and the material of the second red light luminescent layer is two [N-isopropyl-2-(4-fluorophenyl) benzimidazoles ((fbi)
2ir (acac)) 4 of doping, 4'-bis-(9-carbazole) biphenyl (CBP), is expressed as: CBP:(fbi)
2ir (acac), wherein, two [N-isopropyl-2-(4-fluorophenyl) benzimidazoles ((fbi)
2ir (acac)) with 4, the mass ratio of 4'-bis-(9-carbazole) biphenyl (CBP) is 0.02:1, and the thickness of the second red light luminescent layer is 30 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second blue light-emitting is three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr) and tungstic acid (WO
3) 9-(4-2-methyl-2-phenylpropane base)-3 of co-doped, two (triphenyl the silicon)-9H-carbazoles (CzSi) of 6-, are expressed as CzSi:FCNIr:WO
3, wherein, three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr) and 9-(4-2-methyl-2-phenylpropane base)-3, the mass ratio of two (triphenyl the silicon)-9H-carbazoles (CzSi) of 6-is 0.2:1, tungstic acid (WO
3) and 9-(4-2-methyl-2-phenylpropane base)-3, the mass ratio of two (triphenyl the silicon)-9H-carbazoles (CzSi) of 6-is 0.1:1, and the thickness of the second blue light-emitting is 15 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the second luminescence unit is expressed as: CBP:(fbi)
2ir (acac)/CzSi:FCNIr:WO
3.
(6) on the second blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and negative electrode successively, obtain white light organic electroluminescent device: the material of the second electron transfer layer is that 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), thickness is 60 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of electron injecting layer is cesium azide (CsN
3) doping 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), be expressed as: BAlq:CsN
3, wherein, cesium azide (CsN
3) mass ratio that closes aluminium (BAlq) with 4-biphenyl phenolic group-bis-(2-methyl-oxine) is 0.35:1, the thickness of electron injecting layer is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, CsN
3evaporation rate is
the material of negative electrode is gold (Au), and thickness is 200 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
The structure that obtains the present embodiment is SiGe/ glass/SiGe/PI/ITO/SiGe/SnO
2/ CBP:V
2o
5/ CBP/CBP:(fbi)
2ir (acac)/CBP:Ir (mppy)
3/ CzSi:FCNIr:WO
3/ BAlq/WO
3/ CBP:V
2o
5/ CBP/CBP:(fbi)
2ir (acac)/CzSi:FCNIr:WO
3/ BAlq/BAlq:CsN
3the white light organic electroluminescent device of/Au.The luminous efficiency of white light organic electroluminescent device prepared by the present embodiment is in Table 1.
Embodiment 4
The structure of the white light organic electroluminescent device of the present embodiment is: SiGe/ glass/SiGe/PU/ITO/SiGe/SiO
2/ TPD:ReO
3/ TPD/TPD:(F-BT)
2ir (acac)/TPD:Ir (ppy)
3/ 26DCzPPY:FIrtaz:ReO
3/ Alq
3/ ReO
3/ TPD:ReO
3/ TPD/TPD:(F-BT)
2ir (acac)/26DCzPPY:FIrtaz:ReO
3/ Alq
3/ Alq
3: Li
2cO
3/ Ag.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) glass substrate that is 0.4mm by thickness adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On glass substrate two sides, the first anti-reflecting layer and the second anti-reflecting layer are prepared in sputter respectively, and film material is SiGe, and the thickness of the first anti-reflecting layer and the second anti-reflecting layer is 15 nanometers; Choose there is high refractive index transparent polyurethane (PU) film as dioptric layer, one surface of dioptric layer is formed with the projection of a plurality of spaced strips, the cross section of projection is semicircle, and each protruding diameter is 20 microns, and the distance between adjacent two projections is 20 microns; Dioptric layer is formed with to protruding surface and the second anti-reflecting layer pressing, between dioptric layer and the second anti-reflecting layer, forms a plurality of spaces; Then the side surface deposition away from hemispherical projections at dioptric layer forms ITO transparency conducting layer, and the thickness of transparency conducting layer is 100nm; Adopt the mode of magnetron sputtering on transparency conducting layer, to prepare successively the first short reduction layer and the second short reduction layer, the material of the first short reduction layer is SiGe, the material of the second short reduction layer is silicon dioxide, the thickness of the first short reduction layer and the second short reduction layer is 3 nanometers, obtain anode, by anode in 80 ℃ of vacuumizes 15 minutes; The structure of anode is: SiGe/ glass/SiGe/PU/ITO/SiGe/SiO
2.
(2) on the second short reduction layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is rhenium trioxide (ReO
3) doping N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), is expressed as: TPD:ReO
3, wherein, rhenium trioxide (ReO
3) and N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) mass ratio is 0.3:1, and the thickness of the first hole injection layer is 13 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, ReO
3evaporation rate is
the material of the first hole transmission layer is N, N'-bis-(3-aminomethyl phenyl)-N, and N'-diphenyl-4,4'-benzidine (TPD), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(3) vacuum evaporation the first luminescence unit on the first hole transmission layer, the first luminescence unit comprises the first red light luminescent layer, green luminescence layer and the first blue light-emitting, the material of the first red light luminescent layer be two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) ((F-BT)
2ir (acac)) N of doping, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), is expressed as: TPD:(F-BT)
2ir (acac), wherein, two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) closes iridium (III) ((F-BT)
2ir (acac)) and N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, the mass ratio of 4'-benzidine (TPD) is 0.01:1, and the thickness of red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of green luminescence layer is that three (2-phenylpyridines) close iridium (Ir (ppy)
3) doping N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), is expressed as: TPD:Ir (ppy)
3, wherein, three (2-phenylpyridines) close iridium (Ir (ppy)
3) and N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, the mass ratio of 4'-benzidine (TPD) is 0.05:1, and the thickness of green luminescence layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the first blue light-emitting is that two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazoles) are closed iridium (FIrtaz) and rhenium trioxide (ReO
3) co-doped 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY) of 6-, are expressed as 26DCzPPY:Firtaz:ReO
3wherein, two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium (FIrtaz) and 2, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY) of 6-is 0.12:1, rhenium trioxide (ReO
3) with 2, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY) of 6-is 0.07:1, the thickness of the first blue light-emitting is 10 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the first luminescence unit is expressed as: TPD:(F-BT)
2ir (acac)/TPD:Ir (ppy)
3/ 26DCzPPY:FIrtaz:ReO
3.
(4) on the first blue light-emitting, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer: the material of the first electron transfer layer is oxine aluminium (Alq
3), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of charge generation layer is rhenium trioxide (ReO
3), thickness is 20 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole injection layer is rhenium trioxide (ReO
3) doping N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), is expressed as: TPD:ReO
3, wherein, rhenium trioxide (ReO
3) and N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, the mass ratio of 4'-benzidine (TPD) is 0.3:1, and the thickness of the second hole injection layer is 12 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole transmission layer is N, N'-bis-(3-aminomethyl phenyl)-N, and N'-diphenyl-4,4'-benzidine (TPD), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(5) vacuum evaporation the second luminescence unit on the second hole transmission layer, the second luminescence unit comprises the second red light luminescent layer and the second blue light-emitting, the material of the second red light luminescent layer be two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) ((F-BT)
2ir (acac)) N of doping, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), is expressed as: TPD:(F-BT)
2ir (acac), wherein, two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) and N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, the mass ratio of 4'-benzidine (TPD) is 0.01:1, and the thickness of the second red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second blue light-emitting is that two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazoles) are closed iridium (FIrtaz) and rhenium trioxide (ReO
3) co-doped 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY) of 6-, are expressed as 26DCzPPY:Firtaz:ReO
3wherein, two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium (FIrtaz) and 2, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY) of 6-is 0.12:1, rhenium trioxide (ReO
3) with 2, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY) of 6-is 0.07:1, the thickness of the second blue light-emitting is 10 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the second luminescence unit is expressed as: TPD:(F-BT)
2ir (acac)/26DCzPPY:FIrtaz:ReO
3.
(6) on the second blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and negative electrode successively, obtains organic electroluminescence device: the material of the second electron transfer layer is oxine aluminium (Alq
3), thickness is 30 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of electron injecting layer is lithium carbonate (Li
2cO
3) doping oxine aluminium (Alq
3), be expressed as: Alq
3: Li
2cO
3, wherein, lithium carbonate (Li
2cO
3) and oxine aluminium (Alq
3) mass ratio be 0.3:1, the thickness of electron injecting layer is 30 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, Li
2cO
3evaporation rate is
the material of negative electrode is silver (Ag), and thickness is 100 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
The structure that obtains the present embodiment is SiGe/ glass/SiGe/PU/ITO/SiGe/SiO
2/ TPD:ReO
3/ TPD/TPD:(F-BT)
2ir (acac)/TPD:Ir (ppy)
3/ 26DCzPPY:FIrtaz:ReO
3/ Alq
3/ ReO
3/ TPD:ReO
3/ TPD/TPD:(F-BT)
2ir (acac)/26DCzPPY:FIrtaz:ReO
3/ Alq
3/ Alq
3: Li
2cO
3the white light organic electroluminescent device of/Ag.The luminous efficiency of white light organic electroluminescent device prepared by the present embodiment is in Table 1.
Embodiment 5
The structure of the white light organic electroluminescent device of the present embodiment is: SiGe/ glass/SiGe/PU/IZO/SiGe/In
2o
3/ TAPC:MoO
3/ TAPC/TAPC:Ir (btp)
2(acac)/TAPC:Ir (ppy)
2(acac)/35DCzPPY:FIrN4:MoO
3/ TAZ/MoO
3/ TAPC:MoO
3/ TAPC/TAPC:Ir (btp)
2(acac)/35DCzPPY:FIrN4:MoO
3/ TAZ/TAZ:LiF/Al.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) glass substrate that is 0.6mm by thickness adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On glass substrate two sides, the first anti-reflecting layer and the second anti-reflecting layer are prepared in sputter respectively, and film material is SiGe, and the thickness of the first anti-reflecting layer and the second anti-reflecting layer is 15 nanometers; Choose there is high refractive index transparent polyurethane film as dioptric layer, one surface of dioptric layer is formed with the projection of a plurality of spaced strips, the cross section of projection is semicircle, and each protruding diameter is 11 microns, and the distance between adjacent two projections is 11 microns; Dioptric layer is formed with to protruding surface and the second anti-reflecting layer pressing, between dioptric layer and the second anti-reflecting layer, forms a plurality of spaces; Then dioptric layer away from a side surface of hemispherical projections on deposition form indium-zinc oxide (IZO) transparency conducting layer, the thickness of transparency conducting layer is 100nm; Adopt the mode of magnetron sputtering on transparency conducting layer, to prepare successively the first short reduction layer and the second short reduction layer, the material of the first short reduction layer is for being SiGe, the material of the second short reduction layer is indium oxide, the thickness of the first short reduction layer and the second short reduction layer is 3 nanometers, obtain anode, by anode in 80 ℃ of vacuumizes 15 minutes; The structure of anode is: SiGe/ glass/SiGe/PU/IZO/SiGe/In
2o
3.
(2) on the second short reduction layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is molybdenum trioxide (MoO
3) doping 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:MoO
3, wherein, molybdenum trioxide (MoO
3) with 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.25:1, and the thickness of the first hole injection layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, MoO
3evaporation rate is
the material of the first hole transmission layer is 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(3) vacuum evaporation the first luminescence unit on the first hole transmission layer, the first luminescence unit comprises the first red light luminescent layer, green luminescence layer and the first blue light-emitting, and the material of the first red light luminescent layer is that two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp)
2(acac)) 41 of doping, 1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:Ir (btp)
2(acac), wherein, two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp)
2(acac)) with 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.01:1, and the thickness of red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of green luminescence layer is (Ir (ppy)
2(acac)) 1 of doping, 1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:Ir (ppy)
2(acac), wherein, (Ir (ppy)
2(acac)) with 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.07:1, and the thickness of green luminescence layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the first blue light-emitting is that two (4,6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazoliums) close iridium (FIrN4) and molybdenum trioxide (MoO
3) co-doped 3, two (3-(9H-carbazole-9-yl) phenyl) pyridines (35DCzPPY) of 5-, are expressed as 35DCzPPY:FIrN4:MoO
3wherein, two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) closes iridium (FIrN4) and 3, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (35DCzPPY) of 5-is 0.12:1, molybdenum trioxide (MoO
3) with 3, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (35DCzPPY) of 5-is 0.07:1, the thickness of the first blue light-emitting is 10 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the first luminescence unit is expressed as: TAPC:Ir (btp)
2(acac)/TAPC:Ir (ppy)
2(acac)/35DCzPPY:FIrN4:MoO
3.
(4) on the first blue light-emitting, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer: the material of the first electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), thickness is 40 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of charge generation layer is molybdenum trioxide (MoO
3), thickness is 20 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole injection layer is molybdenum trioxide (MoO
3) doping 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:MoO
3, wherein, molybdenum trioxide (MoO
3) with 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.28:1, and the thickness of the second hole injection layer is 13 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole transmission layer is 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(5) vacuum evaporation the second luminescence unit on the second hole transmission layer, the second luminescence unit comprises the second red light luminescent layer and the second blue light-emitting, and the material of the second red light luminescent layer is that two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp)
2(acac)) 1 of doping, 1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:Ir (btp)
2(acac), wherein, two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp)
2(acac)) with 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.01:1, and the thickness of the second red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second blue light-emitting is that two (4,6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazoliums) close iridium (FIrN4) and molybdenum trioxide (MoO
3) co-doped 3, two (3-(9H-carbazole-9-yl) phenyl) pyridines (35DCzPPY) of 5-, are expressed as 35DCzPPY:FIrN4:MoO
3wherein, two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) closes iridium (FIrN4) and 3, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (35DCzPPY) of 5-is 0.12:1, molybdenum trioxide (MoO
3) with 3, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (35DCzPPY) of 5-is 0.07:1, the thickness of the second blue light-emitting is 10 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the second luminescence unit is expressed as: TAPC:Ir (btp)
2(acac)/35DCzPPY:FIrN4:MoO
3.
(6) on the second blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and negative electrode successively, obtain white light organic electroluminescent device: the material of the second electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), thickness is 50 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of electron injecting layer is 3-(biphenyl-4-yl)-5-(4-the tert-butyl-phenyl)-4-phenyl-4H-1 of lithium fluoride (LiF) doping, 2,4-triazole (TAZ), be expressed as: TAZ:LiF, wherein, lithium fluoride (LiF) and 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2, the mass ratio of 4-triazole (TAZ) is 0.3:1, and the thickness of electron injecting layer is 30 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, LiF evaporation rate is
the material of negative electrode is aluminium (Al), and thickness is 100 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
The structure that obtains the present embodiment is SiGe/ glass/SiGe/PU/IZO/SiGe/In
2o
3/ TAPC:MoO
3/ TAPC/TAPC:Ir (btp)
2(acac)/TAPC:Ir (ppy)
2(acac)/35DCzPPY:FIrN4:MoO
3/ TAZ/MoO
3/ TAPC:MoO
3/ TAPC/TAPC:Ir (btp)
2(acac)/35DCzPPY:FIrN4:MoO
3the white light organic electroluminescent device of/TAZ/TAZ:LiF/Al.White light organic electroluminescent device prepared by the present embodiment is at 1000cd/m
2under luminous efficiency in Table 1.
Embodiment 6
The structure of the white light organic electroluminescent device of the present embodiment is: SiGe/ glass/SiGe/PU/AZO/SiGe/ZnS/NPB:WO
3/ NPB/ADN:Ir (piq)
3/ ADN:Ir (mppy)
3/ UGH2:Firpic:V
2o
5/ TPBI/V
2o
5/ NPB:WO
3/ NPB/ADN:Ir (piq)
3/ UGH2:Firpic:V
2o
5/ TPBI/TPBI:Li
2o/Al.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) glass substrate that is 0.5mm by thickness adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On glass substrate two sides, the first anti-reflecting layer and the second anti-reflecting layer are prepared in sputter respectively, and film material is SiGe, and the thickness of the first anti-reflecting layer and the second anti-reflecting layer is 10 nanometers; Choose there is high refractive index transparent polyurethane film as dioptric layer, one surface of dioptric layer is formed with the hemispherical projections of a plurality of spaced strips, the diameter of each hemispherical projections is 18 microns, and the distance between adjacent two hemispherical projections is 18 microns; Dioptric layer is formed with to protruding surface and the second anti-reflecting layer pressing, between dioptric layer and the second anti-reflecting layer, forms a plurality of spaces; Then at dioptric layer, away from a side surface deposition of hemispherical projections, form aluminium zinc oxide (AZO) transparency conducting layer, the thickness of transparency conducting layer is 100nm; Adopt the mode of magnetron sputtering on transparency conducting layer, to prepare successively the first short reduction layer and the second short reduction layer, the material of the first short reduction layer is SiGe, the material of the second short reduction layer is zinc sulphide, the thickness of the first short reduction layer and the second short reduction layer is 2 nanometers, obtain anode, by anode in 80 ℃ of vacuumizes 15 minutes; The structure of anode is: SiGe/ glass/SiGe/PU/AZO/SiGe/ZnS.
(2) on the second short reduction layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is tungstic acid (WO
3) doping N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), is expressed as: NPB:WO
3, wherein, tungstic acid (WO
3) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) mass ratio is 0.3:1, and the thickness of the first hole injection layer is 12 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, WO
3evaporation rate is
the material of the first hole transmission layer is N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(3) vacuum evaporation the first luminescence unit on the first hole transmission layer, the first luminescence unit comprises the first red light luminescent layer, green luminescence layer and the first blue light-emitting, and on the first hole transmission layer, vacuum evaporation forms the first red light luminescent layer, green luminescence layer and the first blue light-emitting successively: the material of the first red light luminescent layer is that three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) doping 9, two (1-naphthyl) anthracenes (ADN) of 10-, are expressed as: ADN:Ir (piq)
3, wherein, three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) with 9, the mass ratio of two (1-naphthyl) anthracenes (ADN) of 10-is 0.01:1, the thickness of red light luminescent layer is 20 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of green luminescence layer is that three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy)
3) doping 9, two (1-naphthyl) anthracenes (ADN) of 10-, are expressed as: ADN:Ir (mppy)
3, wherein, three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy)
3) with 9, the mass ratio of two (1-naphthyl) anthracenes (ADN) of 10-is 0.06:1, the thickness of green luminescence layer is 20 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the first blue light-emitting is that two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls close iridium (FIrpic) and vanadic oxide (V
2o
5) co-doped Isosorbide-5-Nitrae--two (triphenyl silicon) benzene (UGH2), are expressed as UGH2:FIrpic:V
2o
5, wherein, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic) and Isosorbide-5-Nitrae--and the mass ratio of two (triphenyl silicon) benzene (UGH2) is 0.12:1, vanadic oxide (V
2o
5) and Isosorbide-5-Nitrae--the mass ratio of two (triphenyl silicon) benzene (UGH2) is 0.07:1, and the thickness of the first blue light-emitting is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the first luminescence unit is expressed as: ADN:Ir (piq)
3/ ADN:Ir (mppy)
3/ UGH2:Firpic:V
2o
5.
(4) vacuum evaporation the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer on the first blue light-emitting: the material of the first electron transfer layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), thickness is 40 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of charge generation layer is vanadic oxide (V
2o
5), thickness is 20 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole injection layer is tungstic acid (WO
3) doping N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), is expressed as: NPB:WO
3, wherein, tungstic acid (WO
3) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the mass ratio of 4'-diamines (NPB) is 0.3:1, and the thickness of the second hole injection layer is 12 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second hole transmission layer is N, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
(5) vacuum evaporation the second luminescence unit on the second hole transmission layer, the second luminescence unit comprises the second red light luminescent layer and the second blue light-emitting, and on the second hole transmission layer, vacuum evaporation forms the second red light luminescent layer and the second blue light-emitting successively: the material of the second red light luminescent layer is that three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) doping 9, two (1-naphthyl) anthracenes (ADN) of 10-, are expressed as: ADN:Ir (piq)
3, wherein, three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) with 9, the mass ratio of two (1-naphthyl) anthracenes (ADN) of 10-is 0.01:1, the thickness of the second red light luminescent layer is 20 nanometers, the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of the second blue light-emitting is that two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls close iridium (FIrpic) and vanadic oxide (V
2o
5) co-doped Isosorbide-5-Nitrae--two (triphenyl silicon) benzene (UGH2), are expressed as UGH2:FIrpic:V
2o
5, wherein, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic) and Isosorbide-5-Nitrae--and the mass ratio of two (triphenyl silicon) benzene (UGH2) is 0.12:1, vanadic oxide (V
2o
5) and Isosorbide-5-Nitrae--the mass ratio of two (triphenyl silicon) benzene (UGH2) is 0.07:1, and the thickness of the second blue light-emitting is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the second luminescence unit is expressed as: ADN:Ir (piq)
3/ UGH2:Firpic:V
2o
5.
(6) on the second blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and negative electrode successively, obtain organic electroluminescence device: the material of the second electron transfer layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), thickness is 30 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
the material of electron injecting layer is lithia (Li
2o) 1,3 of doping, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), is expressed as: TPBI:Li
2o, wherein, lithia (Li
2o) with 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) mass ratio is 0.3:1, and the thickness of electron injecting layer is 30 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, Li
2o evaporation rate is
the material of negative electrode is aluminium (Al), and thickness is 100 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10
-5pa, evaporation rate is
The structure that obtains the present embodiment is SiGe/ glass SiGe/PU/AZO/SiGe/ZnS/NPB:WO
3/ NPB/ADN:Ir (piq)
3/ ADN:Ir (mppy)
3/ UGH2:Firpic:V
2o
5/ TPBI/V
2o
5/ NPB:WO
3/ NPB/ADN:Ir (piq)
3/ UGH2:Firpic:V
2o
5/ TPBI/TPBI:Li
2the white light organic electroluminescent device of O/Al.White light organic electroluminescent device prepared by the present embodiment is at 1000cd/m
2under luminous efficiency in Table 1.
Table 1 represents is that the white light organic electroluminescent device of embodiment 1～embodiment 6 preparations is at 1000cd/m
2under luminous efficiency data.
Table 1
From table 1, can learn, the white light organic electroluminescent device of embodiment 1～embodiment 6 preparations is at 1000cd/m
2under luminous efficiency be at least 13.7lm/W, and the white light organic electroluminescent device of embodiment 6 preparation is at 1000cd/m
2under luminous efficiency maximum be only 17.4lm/W, and traditional organic electroluminescence device (structure is: ITO/NPB:WO
3/ NPB/ADN:Ir (piq)
3/ ADN:Ir (mppy)
3/ UGH2:Firpic/TPBI/V
2o
5/ NPB:WO
3/ NPB/ADN:Ir (piq)
3/ UGH2:Firpic/TPBI/TPBI:Li
2o/Al) at 1000cd/m
2under luminous efficiency maximum be only 10lm/W, illustrate that the organic electroluminescence device of embodiment 1～embodiment 6 preparation has less operating current.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a white light organic electroluminescent device, it is characterized in that, comprise the anode, the first hole injection layer, the first hole transmission layer, the first luminescence unit, the first electron transfer layer, charge generation layer, the second hole injection layer, the second hole transmission layer, the second luminescence unit, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described anode comprises the first anti-reflecting layer, glass substrate, the second anti-reflecting layer, dioptric layer, transparency conducting layer, the first short reduction layer and the second short reduction layer stacking gradually, and the material of described the first anti-reflecting layer and described the second anti-reflecting layer is SiGe, described dioptric layer is formed with the projection of a plurality of spaced strips near the surface of described the second anti-reflecting layer, the cross section of described projection is semicircle, the end of described projection and described the second anti-reflecting layer butt and be bonded together, described transparency conducting layer is laminated in described dioptric layer away from a side of described projection, and the material of described the first short reduction layer is SiGe, and the material of described the second short reduction layer is selected from least one of indium oxide, zinc sulphide, tin oxide and silicon dioxide, described the first hole injection layer is laminated on described the second short reduction layer, described the first luminescence unit comprises the first red light luminescent layer, green luminescence layer and the first blue light-emitting stacking gradually, and described the first red light luminescent layer is laminated on described the first hole transmission layer, described the second luminescence unit comprises the second red light luminescent layer and is laminated in the second blue light-emitting on described the second red light luminescent layer, and described the second red light luminescent layer is laminated on described the second hole transmission layer, the material of described the first blue light-emitting comprises the first Blue-light emitting host material, be entrained in the first blue light guest materials and the first charge generating material in described the first Blue-light emitting host material, the mass ratio of described the first blue light guest materials and described the first Blue-light emitting host material is 0.05～0.2:1, the mass ratio of described the first charge generating material and described the first Blue-light emitting host material is 0.05～0.1:1, the material of described the second blue light-emitting comprises the second Blue-light emitting host material, be entrained in the second blue light guest materials and the second charge generating material in described the second Blue-light emitting host material, the mass ratio of described the second blue light guest materials and described the second Blue-light emitting host material is 0.05～0.2:1, the mass ratio of described the second charge generating material and described the second Blue-light emitting host material is 0.05～0.1:1, described the first Blue-light emitting host material and described the second Blue-light emitting host material are selected from 4,4'-bis-(9-carbazole) biphenyl, 9,9'-(1,3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles, 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines, 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine and the Isosorbide-5-Nitraes of 5---at least one in two (triphenyl silicon) benzene, described the first blue light guest materials and described the second blue light guest materials are selected from two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium, two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium and two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) closes at least one in iridium, described the first charge generating material and described the second charge generating material are selected from molybdenum trioxide, tungstic acid, at least one in vanadic oxide and rhenium trioxide,
The material of described charge generation layer is selected from least one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide.
2. white light organic electroluminescent device according to claim 1, is characterized in that, the material of described dioptric layer is that refractive index is 1.7～1.9 overlay; Each protruding diameter is 5 microns～20 microns, and the distance between adjacent two projections is 5 microns～20 microns; Described the first anti-reflecting layer and the second anti-reflecting layer thickness are 10 nanometer～20 nanometers; The material of described transparency conducting layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide, and thickness is 80～150 nanometers; The thickness of described the first short reduction layer and described the second short reduction layer is 2 nanometer～5 nanometers.
3. white light organic electroluminescent device according to claim 1, it is characterized in that, the material of described the first red light luminescent layer comprises the first ruddiness material of main part and is doped in the first ruddiness guest materials in described the first ruddiness material of main part, and the mass ratio of described the first ruddiness guest materials and described the first ruddiness material of main part is 0.005～0.02:1, the material of described the second red light luminescent layer comprises the second ruddiness material of main part and is doped in the second ruddiness guest materials in described the second ruddiness material of main part, and the mass ratio of described the second ruddiness guest materials and described the second ruddiness material of main part is 0.005～0.02:1, described the first ruddiness material of main part and described the second ruddiness material of main part are selected from 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] cyclohexane and 9, at least one in two (1-naphthyl) anthracenes of 10-, described the first ruddiness guest materials and described the second ruddiness guest materials are selected from two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III), two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) and three (1-phenyl-isoquinolin) and close at least one in iridium,
The material of described green luminescence layer comprises green glow material of main part and is doped in the green glow guest materials in described green glow material of main part, and the mass ratio of described green glow guest materials and described green glow material of main part is 0.02～0.10:1; Described green glow material of main part is selected from 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in two (1-naphthyl) anthracenes of cyclohexane and 9,10-; Described green glow guest materials is selected from that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium and three [2-(p-methylphenyl) pyridine] closes at least one in iridium (III).
4. white light organic electroluminescent device according to claim 1, is characterized in that, the thickness of described the first red light luminescent layer is 10 nanometer～30 nanometers; The thickness of described green luminescence layer is 10 nanometer～30 nanometers; The thickness of described the first blue light-emitting is 5 nanometer～15 nanometers; The thickness of described the second red light luminescent layer is 10 nanometer～30 nanometers; The thickness of described the second blue light-emitting is 5 nanometer～15 nanometers.
5. white light organic electroluminescent device according to claim 1, it is characterized in that, the material of described the first hole injection layer comprises hole mobile material and is doped in the p-type dopant material in described hole mobile material, and the mass ratio of p-type dopant material described in described the first hole injection layer and described hole mobile material is 0.25～0.35:1; The material of described the second hole injection layer comprises hole mobile material and is doped in the p-type dopant material in described hole mobile material, and the mass ratio of p-type dopant material described in described the second hole injection layer and described hole mobile material is 0.25～0.35:1; Described hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane; Described p-type dopant material is selected from least one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide;
The material of the material of described the first hole transmission layer and described the second hole transmission layer is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine and 1,1-bis-[4-[N, N'-bis-(p-tolyl) amino] phenyl] at least one in cyclohexane;
The material of the material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described electron injecting layer comprises electron transport material and is doped in the N-shaped dopant material in described electron transport material, and the mass ratio of described N-shaped dopant material and described electron transport material is 0.25～0.35:1; Described electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; Described N-shaped dopant material is selected from least one in cesium carbonate, cesium fluoride, cesium azide, lithium carbonate, lithium fluoride and lithia; And
The material of described negative electrode is selected from least one in silver, aluminium and gold.
6. a preparation method for white light organic electroluminescent device, is characterized in that, comprises the steps:
On glass substrate two sides, the first anti-reflecting layer and the second anti-reflecting layer are prepared in sputter respectively;
Dioptric layer is pressed on the second anti-reflecting layer of glass substrate, described dioptric layer is formed with the projection of a plurality of spaced strips near the surface of described the second anti-reflecting layer, the cross section of described projection is semicircle, the end of described projection and described the second anti-reflecting layer butt and be bonded together;
A side surface deposit transparent conductive layer at described dioptric layer away from described projection;
On described transparency conducting layer, magnetron sputtering is prepared the first short reduction layer and the second short reduction layer successively, and described the first anti-reflecting layer, glass substrate, the second anti-reflecting layer, dioptric layer, transparency conducting layer, the first short reduction layer and the second short reduction layer form anode;
On described the second short reduction layer, evaporation is prepared the first hole injection layer and the first hole transmission layer successively;
Evaporation the first luminescence unit on described the first hole transmission layer, described the first luminescence unit comprises the first red light luminescent layer, green luminescence layer and the first blue light-emitting stacking gradually, wherein, the material of described the first blue light-emitting comprises the first Blue-light emitting host material, be entrained in the first blue light guest materials and the first charge generating material in described the first Blue-light emitting host material, the mass ratio of described the first blue light guest materials and described the first Blue-light emitting host material is 0.05～0.2:1, the mass ratio of described the first charge generating material and described the first Blue-light emitting host material is 0.05～0.1:1, described the first Blue-light emitting host material is selected from 4, 4'-bis-(9-carbazole) biphenyl, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-, 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 6-, 3, two (3-(9H-carbazole-9-yl) phenyl) pyridines and 1 of 5-, at least one in two (triphenyl silicon) benzene of 4--, described the first blue light guest materials is selected from two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium, two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium and two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) closes at least one in iridium, described the first charge generating material is selected from molybdenum trioxide, tungstic acid, at least one in vanadic oxide and rhenium trioxide,
At described the first blue light-emitting surface evaporation, prepare the first electron transfer layer;
At described the first electron transfer layer surface evaporation, prepare charge generation layer, the material of described charge generation layer is selected from least one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide;
On described charge generation layer surface, evaporation is prepared the second hole injection layer and the second hole transmission layer;
At described the second hole transmission layer surface evaporation, prepare the second luminescence unit, described the second luminescence unit comprises the second red light luminescent layer and the second blue light-emitting, the material of described the second blue light-emitting comprises the second Blue-light emitting host material, be entrained in the second blue light guest materials and the second charge generating material in described the second Blue-light emitting host material, the mass ratio of described the second blue light guest materials and described the first Blue-light emitting host material is 0.05～0.2:1, the mass ratio of described the second charge generating material and described the second Blue-light emitting host material is 0.05～0.1:1, described the second Blue-light emitting host material is selected from 4, 4'-bis-(9-carbazole) biphenyl, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-, 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 6-, 3, two (3-(9H-carbazole-9-yl) phenyl) pyridines and 1 of 5-, at least one in two (triphenyl silicon) benzene of 4--, described the second blue light guest materials is selected from two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5'-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium, two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium and two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) closes at least one in iridium, described the second charge generating material is selected from molybdenum trioxide, tungstic acid, at least one in vanadic oxide and rhenium trioxide, and
On described the second blue light-emitting surface successively evaporation, prepare the second electron transfer layer, electron injecting layer and negative electrode, obtain white light organic electroluminescent device.
7. the preparation method of white light organic electroluminescent device according to claim 6, is characterized in that, also comprises the step that described glass substrate is cleaned before refraction index layer being pressed on the second anti-reflecting layer of glass substrate; The step of described cleaning is: glass substrate is adopted to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, and then dry, more clean glass substrate is carried out to surface activation process.
8. the preparation method of white light organic electroluminescent device according to claim 6, it is characterized in that, the material of described the first short reduction layer is SiGe, the material of described the second short reduction layer is selected from least one of indium oxide, zinc sulphide, tin oxide and silicon dioxide, and the thickness of described the first short reduction layer and described the second short reduction layer is 2 nanometer～5 nanometers.
9. the preparation method of white light organic electroluminescent device according to claim 6, it is characterized in that, on described the second short reduction layer, evaporation forms before described the first hole injection layer first described anode in 60 ℃～80 ℃ vacuumizes 15 minutes～30 minutes.
10. the preparation method of white light organic electroluminescent device according to claim 6, is characterized in that, the material of described dioptric layer is that refractive index is 1.7～1.9 transparent plastic; Each protruding diameter is 5 microns～20 microns, and the distance between adjacent two projections is 5 microns～20 microns; The material of described transparency conducting layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide, and the thickness of described transparency conducting layer is 80～150 nanometers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310192553.7A CN104183755A (en) | 2013-05-22 | 2013-05-22 | White-light organic light-emitting device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310192553.7A CN104183755A (en) | 2013-05-22 | 2013-05-22 | White-light organic light-emitting device and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104183755A true CN104183755A (en) | 2014-12-03 |
Family
ID=51964653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310192553.7A Pending CN104183755A (en) | 2013-05-22 | 2013-05-22 | White-light organic light-emitting device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104183755A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050248267A1 (en) * | 2002-09-20 | 2005-11-10 | Matsushita Electric Industrial Co., Ltd. | Organic electroluminescence element and an exposure unit and image-forming apparatus both using the element |
| CN1943277A (en) * | 2004-02-18 | 2007-04-04 | 索尼株式会社 | Display element |
| CN1947277A (en) * | 2004-04-22 | 2007-04-11 | 肖特股份公司 | Organic, electro-optical element with increased decoupling efficiency |
| CN101682001A (en) * | 2007-05-10 | 2010-03-24 | 伊斯曼柯达公司 | Electroluminescent device having improved light output |
| US7687990B2 (en) * | 2007-04-12 | 2010-03-30 | Global Oled Technology Llc | OLED device with short reduction |
| CN101960639A (en) * | 2008-02-29 | 2011-01-26 | 全球Oled科技有限责任公司 | OLED devices with short-circuit reducing layers |
| CN102655219A (en) * | 2012-02-23 | 2012-09-05 | 京东方科技集团股份有限公司 | Multicolour OLED (organic light-emitting diode), multicolour OLED unit and display device |
-
2013
- 2013-05-22 CN CN201310192553.7A patent/CN104183755A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050248267A1 (en) * | 2002-09-20 | 2005-11-10 | Matsushita Electric Industrial Co., Ltd. | Organic electroluminescence element and an exposure unit and image-forming apparatus both using the element |
| CN1943277A (en) * | 2004-02-18 | 2007-04-04 | 索尼株式会社 | Display element |
| CN1947277A (en) * | 2004-04-22 | 2007-04-11 | 肖特股份公司 | Organic, electro-optical element with increased decoupling efficiency |
| US7687990B2 (en) * | 2007-04-12 | 2010-03-30 | Global Oled Technology Llc | OLED device with short reduction |
| CN101682001A (en) * | 2007-05-10 | 2010-03-24 | 伊斯曼柯达公司 | Electroluminescent device having improved light output |
| CN101960639A (en) * | 2008-02-29 | 2011-01-26 | 全球Oled科技有限责任公司 | OLED devices with short-circuit reducing layers |
| CN102655219A (en) * | 2012-02-23 | 2012-09-05 | 京东方科技集团股份有限公司 | Multicolour OLED (organic light-emitting diode), multicolour OLED unit and display device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104518117A (en) | Organic light emitting diode device and preparation method thereof | |
| CN104078611A (en) | White organic light-emitting diode and manufacturing method thereof | |
| CN104882545A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104183722A (en) | White-light organic light emission diode and preparation method thereof | |
| CN104183721A (en) | Organic light emitting diode and preparation method thereof | |
| CN104183746A (en) | White light organic light emitting device and manufacturing method thereof | |
| CN104078604A (en) | White organic light-emitting diode and manufacturing method thereof | |
| CN104078571A (en) | White organic light-emitting diode and manufacturing method thereof | |
| CN103633247A (en) | White light organic electroluminescent device and preparation method thereof | |
| CN104183754A (en) | Organic light-emitting device and preparation method thereof | |
| CN104183770A (en) | White-light organic light emission diode and preparation method thereof | |
| CN104078622A (en) | Organic light-emitting diode device and manufacturing method thereof | |
| CN103682137A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104078576A (en) | White organic light-emitting diode and manufacturing method thereof | |
| CN104078572A (en) | White organic light-emitting diode and manufacturing method thereof | |
| CN103579525A (en) | Organic electroluminescence device and preparation method thereof | |
| CN104078578A (en) | Organic light-emitting diode device and manufacturing method thereof | |
| CN104183723A (en) | Organic light emitting diode and preparation method thereof | |
| CN104518116A (en) | Organic light emitting diode device and preparation method thereof | |
| CN104183755A (en) | White-light organic light-emitting device and preparation method thereof | |
| CN104183589A (en) | White organic light emitting device and manufacturing method thereof | |
| CN104183717A (en) | Organic light-emitting device and preparation method thereof | |
| CN104078616A (en) | Organic light-emitting diode device and manufacturing method thereof | |
| CN104078617A (en) | Organic light-emitting diode device and manufacturing method thereof | |
| CN104078605A (en) | Organic light-emitting diode device and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141203 |