CN104518150A - Organic electroluminescent device and method for preparing same - Google Patents
Organic electroluminescent device and method for preparing same Download PDFInfo
- Publication number
- CN104518150A CN104518150A CN201310452689.7A CN201310452689A CN104518150A CN 104518150 A CN104518150 A CN 104518150A CN 201310452689 A CN201310452689 A CN 201310452689A CN 104518150 A CN104518150 A CN 104518150A
- Authority
- CN
- China
- Prior art keywords
- metal
- doped layer
- layer
- sodium salt
- organic
- 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
- 238000000034 method Methods 0.000 title claims description 6
- 239000000463 material Substances 0.000 claims abstract description 142
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 69
- 239000007769 metal material Substances 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 238000002347 injection Methods 0.000 claims abstract description 31
- 239000007924 injection Substances 0.000 claims abstract description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 26
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 19
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000011780 sodium chloride Substances 0.000 claims abstract description 13
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 7
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000008020 evaporation Effects 0.000 claims description 87
- 238000001704 evaporation Methods 0.000 claims description 87
- 238000005401 electroluminescence Methods 0.000 claims description 40
- 229910000765 intermetallic Inorganic materials 0.000 claims description 35
- 238000005566 electron beam evaporation Methods 0.000 claims description 28
- 238000007747 plating Methods 0.000 claims description 28
- 230000005540 biological transmission Effects 0.000 claims description 24
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000011368 organic material Substances 0.000 claims description 17
- 238000005516 engineering process Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010931 gold Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 11
- 229960004643 cupric oxide Drugs 0.000 claims description 11
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 8
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 8
- 238000004770 highest occupied molecular orbital Methods 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract 2
- 230000005525 hole transport Effects 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 1
- 238000002161 passivation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 180
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 14
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 12
- 238000010276 construction Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 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 6
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 6
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000003574 free electron Substances 0.000 description 6
- RAPHUPWIHDYTKU-WXUKJITCSA-N 9-ethyl-3-[(e)-2-[4-[4-[(e)-2-(9-ethylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]carbazole Chemical compound C1=CC=C2C3=CC(/C=C/C4=CC=C(C=C4)C4=CC=C(C=C4)/C=C/C=4C=C5C6=CC=CC=C6N(C5=CC=4)CC)=CC=C3N(CC)C2=C1 RAPHUPWIHDYTKU-WXUKJITCSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HXWWMGJBPGRWRS-CMDGGOBGSA-N 4- -2-tert-butyl-6- -4h-pyran Chemical compound O1C(C(C)(C)C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(C(CCN2CCC3(C)C)(C)C)=C2C3=C1 HXWWMGJBPGRWRS-CMDGGOBGSA-N 0.000 description 4
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000000075 oxide glass Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 235000003642 hunger Nutrition 0.000 description 3
- 230000037351 starvation Effects 0.000 description 3
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- MQCHTHJRANYSEJ-UHFFFAOYSA-N n-[(2-chlorophenyl)methyl]-1-(3-methylphenyl)benzimidazole-5-carboxamide Chemical compound CC1=CC=CC(N2C3=CC=C(C=C3N=C2)C(=O)NCC=2C(=CC=CC=2)Cl)=C1 MQCHTHJRANYSEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- DDYSHSNGZNCTKB-UHFFFAOYSA-N gold(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Au+3].[Au+3] DDYSHSNGZNCTKB-UHFFFAOYSA-N 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- H10K50/805—Electrodes
- H10K50/82—Cathodes
-
- 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
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/166—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using selective deposition, e.g. using a mask
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Provided is an organic electroluminescent device, comprising an anode, a hole injection layer, a hole transport layer, a luminous layer, an electron transfer layer, an electron injection layer, and a cathode stacked in sequence. A cathode layer is formed by a sodium salt doping layer, a first metal doping layer, and a second metal doping layer. The sodium salt doping layer contains a sodium salt material and an organic electron transport material doped in the sodium salt material. The sodium salt material is selected from at least one of sodium carbonate, sodium chloride, sodium fluoride, and sodium bromide. The first metal doping layer contains a first metal material and VB group metallic compounds doped in the first metal material. The VB group metallic compounds are selected from at least one of tantalum pentoxide, vanadium pentoxide, and niobium pentoxide. The second metal doping layer contains a second metal material and a passivation material doped in the second metal material. The luminescence efficiency of the organic electroluminescent device is high. The invention also provides a preparation method for the organic electroluminescent device.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Under the principle of luminosity of organic electroluminescence device is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
The negative electrode of traditional organic electroluminescence device is generally the metal such as silver (Ag), gold (Au), and after preparation, negative electrode very easily penetrates into organic layer, damage, electronics easy cancellation near negative electrode, thus luminous efficiency is lower to organic layer.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the anode stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described cathode layer is by sodium salt doped layer, first metal-doped layer and the second metal-doped layer composition, described sodium salt doped layer comprises sodium salt material and is entrained in the Organic Electron Transport Material in described sodium salt material, described sodium salt material is selected from sodium carbonate, sodium chloride, at least one in sodium fluoride and sodium bromide, described Organic Electron Transport Material HOMO energy level is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, described first metal-doped layer comprises the first metal material and is entrained in the VB race metallic compound in described first metal material, described the first metal layer material work functions is-2.0eV ~-3.5eV, described VB race metallic compound is selected from tantalum pentoxide, at least one in vanadic oxide and niobium pentaoxide, described second metal-doped layer comprises the second metal material and is entrained in the passivating material in described second metal material, described second metal material work function is-4.0eV ~-5.5eV, described passivating material is selected from silicon dioxide, aluminium oxide, at least one in nickel oxide and cupric oxide.
Described first metal material is selected from least one in magnesium, strontium, calcium and ytterbium, and described second metal material is selected from least one in silver, aluminium, platinum and gold, and described Organic Electron Transport Material is selected from 1,2,4-triazole derivative, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles], 2,9-dimethyl-4,7-biphenyl-1, at least one in 10-phenanthrolene and 2,8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene.
Described in described sodium salt doped layer material, the mass ratio of sodium salt material and described Organic Electron Transport Material is 5: 1 ~ 15: 1, the mass ratio of the first metal material described in described first metal-doped layer and described VB race metallic compound is 10: 1 ~ 20: 1, and the mass ratio of described second metal material and described passivating material is 1: 1 ~ 5: 1.
Described sodium salt doped layer thickness is 5nm ~ 300nm, and described first metal-doped layer thickness is 10nm ~ 50nm, and described second metal-doped layer thickness is 100nm ~ 300nm.
A preparation method for organic electroluminescence device, comprises the following steps:
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is formed successively at anode surface; And
Sodium salt doped layer is prepared by the method for thermal resistance evaporation on electron injecting layer surface, described sodium salt doped layer comprises sodium salt material and is entrained in the Organic Electron Transport Material in described sodium salt material, described sodium salt material is selected from sodium carbonate, sodium chloride, at least one in sodium fluoride and sodium bromide, described Organic Electron Transport Material HOMO energy level is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, then the first metal-doped layer is prepared on described sodium salt doped layer surface by electron beam evaporation plating mode, described first metal-doped layer comprises the first metal material and is entrained in the VB race metallic compound in described first metal material, described the first metal layer material work functions is-2.0eV ~-3.5eV, described VB race metallic compound is selected from tantalum pentoxide, at least one in vanadic oxide and niobium pentaoxide, described second metal-doped layer is prepared at described first metal-doped layer surface evaporation by the mode of electron beam evaporation plating, described second metal-doped layer comprises the second metal material and is entrained in the passivating material in described second metal material, described second metal material work function is-4.0eV ~-5.5eV, described passivating material is selected from silicon dioxide, aluminium oxide, at least one in nickel oxide and cupric oxide.
Described first metal material is selected from least one in magnesium, strontium, calcium and ytterbium, and described second metal material is selected from least one in silver, aluminium, platinum and gold, and described Organic Electron Transport Material is selected from 1,2,4-triazole derivative, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles], 2,9-dimethyl-4,7-biphenyl-1, at least one in 10-phenanthrolene and 2,8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene.
Described in described sodium salt doped layer material, the mass ratio of sodium salt material and described Organic Electron Transport Material is 5: 1 ~ 15: 1, the mass ratio of the first metal material described in described first metal-doped layer and described VB race metallic compound is 10: 1 ~ 20: 1, and the mass ratio of described second metal material and described passivating material is 1: 1 ~ 5: 1.
Described sodium salt doped layer thickness is 5nm ~ 300nm, and the first metal-doped layer thickness is 10nm ~ 50nm, and described second metal-doped layer thickness is 100nm ~ 300nm.
The concrete technology condition of described thermal resistance evaporation mode is: operating pressure is 2 × 10
-3pa ~ 5 × 10
-5pa, operating current is 1A ~ 3A, and the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
The concrete technology condition of described electron beam evaporation plating mode is: operating pressure is 2 × 10
-3~ 5 × 10
-5pa, the energy density of electron beam evaporation plating is 10W/cm
2~ l00W/cm
2, the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device and preparation method thereof, by preparing the cathode construction of sandwich construction, this cathode construction layer is by sodium salt doped layer, first metal-doped layer and the second metal-doped layer composition, sodium salt material and crystallinity Organic Electron Transport Material form, the work function of sodium salt material close to organic material LUMO relatively, the injection barrier of electronics can be reduced, improve the injection efficiency of electronics, crystalline material makes film surface form wave structure, make the light scattering of Vertical Launch, no longer vertical, thus can not be coupled with the free electron of metal level (parallel free electron can be coupled with vertical photon and lose), improve photon utilance, simultaneously, material has electronic transmission performance, the transmission rate of electronics can be improved, then one deck first metal-doped layer is prepared, be made up of the metal of low-function function and VB race metallic compound composition material, low workfunction metal has lower work function, electronic barrier can be reduced further and improve electron injection efficiency, and can carrier concentration be improved thus improve conductivity, VB race element transmitance in visible-range is higher, finally prepare one deck second metal-doped layer, be made up of high-work-function metal and passivating material, high-work-function metal free electronic concentration is larger, can further improve conductivity, the reflection of light can be improved simultaneously, passivating material effectively can improve the stability of device, starvation and steam enter into device, this composite cathode effectively can improve luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the cathode construction schematic diagram of the organic electroluminescence device of an execution mode;
Fig. 3 is brightness and the luminous efficiency graph of a relation of organic electroluminescence device prepared by embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is illustrated further.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises the anode 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and the negative electrode 70 that stack gradually.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium, is preferably ITO.
Hole injection layer 20 is formed at anode 10 surface.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably MoO
3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.
Hole transmission layer 30 is formed at the surface of hole injection layer 20.The material of hole transmission layer 30 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of hole transmission layer 30 is 20nm ~ 60nm, is preferably 30nm.
Luminescent layer 40 is formed at the surface of hole transmission layer 30.The material of luminescent layer 40 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 12nm.
Electron transfer layer 50 is formed at the surface of luminescent layer 40.The material of electron transfer layer 50 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of electron transfer layer 50 is 40nm ~ 300nm, is preferably 120nm.
Electron injecting layer 60 is formed at electron transfer layer 50 surface.The material of electron injecting layer 60 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.
Be the cathode construction schematic diagram of the organic electroluminescence device of an execution mode please refer to Fig. 2, negative electrode 70 is formed at electron injecting layer 60 surface.Cathode layer 70 is made up of sodium salt doped layer 701, first metal-doped layer 702 and the second metal-doped layer 703, described sodium salt doped layer 701 comprises sodium salt material and is entrained in the Organic Electron Transport Material in described sodium salt material, and described sodium salt material is selected from sodium carbonate (Na
2cO
3), sodium chloride (NaCl), sodium fluoride (NaF) and the middle at least one of sodium bromide (NaBr), described Organic Electron Transport Material HOMO energy level is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, specifically be selected from 1, 2, 4-triazole derivative (TAZ), 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles] (OXD-7), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP) and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] the middle at least one of thiophene (PO15), first metal-doped layer 702 comprises the first metal material and is entrained in the VB race metallic compound in described first metal material, described the first metal layer material work functions is-2.0eV ~-3.5eV, specifically be selected from magnesium (Mg), strontium (Sr), calcium (Ca) and the middle at least one of ytterbium (Yb), described VB race metallic compound is selected from tantalum pentoxide (Ta
2o
5), vanadic oxide (V
2o
5) and niobium pentaoxide (Nb
2o
5) middle at least one, second metal-doped layer 703 comprises the second metal material and is entrained in the passivating material in described second metal material, described second metal material work function is-4.0eV ~-5.5eV, specifically be selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), described passivating material is selected from silicon dioxide (SiO2), aluminium oxide (Al
2o
3), at least one in nickel oxide (NiO) and cupric oxide (CuO).
Described in described sodium salt doped layer 701 material, the mass ratio of sodium salt material and described Organic Electron Transport Material is 5: 1 ~ 15: 1, described in described first metal-doped layer 702, the mass ratio of the first metal material and described VB race metallic compound is 10: 1 ~ 20: 1, and described in described second metal-doped layer 703, the mass ratio of the second metal material and described passivating material is 1: 1 ~ 5: 1.
Described sodium salt doped layer thickness is 5nm ~ 300nm, and described first metal-doped layer thickness is 10nm ~ 50nm, and described second metal-doped layer thickness is 100nm ~ 300nm.
Above-mentioned organic electroluminescence device 100 is by preparing the cathode construction of sandwich construction, this cathode construction layer is by sodium salt doped layer, first metal-doped layer and the second metal-doped layer composition, sodium salt material and crystallinity Organic Electron Transport Material form, the work function of sodium salt material close to organic material LUMO relatively, the injection barrier of electronics can be reduced, improve the injection efficiency of electronics, crystalline material makes film surface form wave structure, make the light scattering of Vertical Launch, no longer vertical, thus can not be coupled with the free electron of metal level (parallel free electron can be coupled with vertical photon and lose), improve photon utilance, simultaneously, material has electronic transmission performance, the transmission rate of electronics can be improved, then one deck first metal-doped layer is prepared, be made up of the metal of low-function function and VB race metallic compound composition material, low workfunction metal has lower work function, electronic barrier can be reduced further and improve electron injection efficiency, and can carrier concentration be improved thus improve conductivity, VB race element transmitance in visible-range is higher, finally prepare one deck second metal-doped layer, be made up of high-work-function metal and passivating material, high-work-function metal free electronic concentration is larger, can further improve conductivity, the reflection of light can be improved simultaneously, passivating material effectively can improve the stability of device, starvation and steam enter into device, this composite cathode effectively can improve luminous efficiency.
Be appreciated that in this organic electroluminescence device 100 and also can other functional layers be set as required.
The preparation method of the organic electroluminescence device 100 of one embodiment, it comprises the following steps:
Step S110, form hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50 and electron injecting layer 60 successively on anode 10 surface.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium, is preferably ITO.
In present embodiment, before anode 10 surface forms hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution on anode 10 surface.
Hole injection layer 20 is formed at the surface of anode 10.Hole injection layer 20 is prepared by evaporation.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably MoO
3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Hole transmission layer 30 is formed at the surface of hole injection layer 20.Hole-injecting Buffer Layer for Improvement 30 is prepared by evaporation.The material of hole transmission layer 30 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of hole transmission layer 30 is 20nm ~ 60nm, is preferably 30nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Luminescent layer 40 is formed at the surface of hole transmission layer 30.Luminescent layer 40 is prepared by evaporation.The material of luminescent layer 40 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 0.5nm ~ 40nm, is preferably 12nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron transfer layer 50 is formed at the surface of luminescent layer 40.The material of electron transfer layer 50 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of electron transfer layer 50 is 40nm ~ 300nm, is preferably 120nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron injecting layer 60 is formed at electron transfer layer 50 surface.Electron injecting layer 60 is prepared by evaporation.The material of electron injecting layer 60 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Step S120, electron injecting layer surface prepare sodium salt doped layer 701 by the method for thermal resistance evaporation, described sodium salt doped layer 701 comprises sodium salt material and is entrained in the Organic Electron Transport Material in described sodium salt material, and described sodium salt material is selected from sodium carbonate (Na
2cO
3), sodium chloride (NaCl), sodium fluoride (NaF) and the middle at least one of sodium bromide (NaBr), described Organic Electron Transport Material HOMO energy level is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, specifically be selected from 1, 2, 4-triazole derivative (TAZ), 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles] (OXD-7), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP) and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] the middle at least one of thiophene (PO15), then the first metal-doped layer 702 is prepared on described sodium salt doped layer surface by electron beam evaporation plating mode, first metal-doped layer 702 comprises the first metal material and is entrained in the VB race metallic compound in described first metal material, described the first metal layer material work functions is-2.0eV ~-3.5eV, specifically be selected from magnesium (Mg), strontium (Sr), calcium (Ca) and the middle at least one of ytterbium (Yb), described VB race metallic compound is selected from tantalum pentoxide (Ta
2o
5), vanadic oxide (V
2o
5) and niobium pentaoxide (Nb
2o
5) middle at least one, described second metal-doped layer is prepared at described first metal-doped layer surface evaporation by the mode of electron beam evaporation plating, second metal-doped layer 703 comprises the second metal material and is entrained in the passivating material in described second metal material, described second metal material work function is-4.0eV ~-5.5eV, specifically be selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), described passivating material is selected from silicon dioxide (SiO
2), aluminium oxide (Al
2o
3), at least one in nickel oxide (NiO) and cupric oxide (CuO).
Described in described sodium salt doped layer 701 material, the mass ratio of sodium salt material and described Organic Electron Transport Material is 5: 1 ~ 15: 1, described in described first metal-doped layer 702, the mass ratio of the first metal material and described VB race metallic compound is 10: 1 ~ 20: 1, and described in described second metal-doped layer 703, the mass ratio of the second metal material and described passivating material is 1: 1 ~ 5: 1.
Described sodium salt doped layer thickness is 5nm ~ 300nm, and described first metal-doped layer thickness is 10nm ~ 50nm, and described second metal-doped layer thickness is 100nm ~ 300nm.
The concrete technology condition of described thermal resistance evaporation mode is: operating pressure is 2 × 10
-3pa ~ 5 × 10
-5pa, operating current is 1A ~ 3A, and the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
The concrete technology condition of described electron beam evaporation plating mode is: operating pressure is 2 × 10
-3~ 5 × 10
-5pa, the energy density of electron beam evaporation plating is 10W/cm
2~ l00W/cm
2, the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device preparation method, technique is simple, and the luminous efficiency of the organic electroluminescence device of preparation is higher.
Below in conjunction with specific embodiment, the preparation method to organic electroluminescence device provided by the invention is described in detail.
The embodiment of the present invention and the preparation used by 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, the Keithley2400 of Keithley company of the U.S. tests electric property.
Embodiment 1
Structure prepared by the present embodiment is ITO/MoO
3/ NPB/Alq
3/ Bphen/LiF/NaCl:TAZ/Mg:Ta
2o
5/ Pt:SiO
2organic electroluminescence device, "/" presentation layer in the present embodiment and following examples, ": " represents doping.
First ITO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Clean up and carry out suitable process to conductive substrates afterwards: oxygen plasma treatment, the processing time is 5min, and power is 30W; Evaporation hole injection layer, material is MoO
3, thickness is 60nm; Evaporation hole transmission layer, material is NPB, and thickness is 50nm; Evaporation luminescent layer, material is BCzVBi, and thickness is 30nm; Evaporation electron transfer layer, material is Bphen, and thickness is 160nm; Evaporation electron injecting layer, material is LiF, and thickness is 0.7nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare sodium salt doped layer at described electron injecting layer surface evaporation, material is NaCl: TAZ, NaCl and TAZ mass ratio is 10: 1, thickness is 100nm, then prepares the first metal-doped layer by electron beam evaporation plating, and material is Mg:Ta
2o
5, Mg and Ta
2o
5mass ratio be 12: 1, thickness is 30nm, and then being prepared by electron beam evaporation plating mode has the second metal-doped layer, and material is Pt:SiO
2, Pt and SiO
2mass ratio be 3: 1, thickness is 200nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 8 × 10
-5pa, the energy density of electron beam evaporation plating is 30W/cm
2, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s;
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 8 × 10
-5pa, operating current is 1A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s.
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is ITO/MoO
3/ NPB/Alq
3/ Bphen/LiF/NaCl:TAZ/Mg:Ta
2o
5/ Pt:SiO
2the structure prepared of organic electroluminescence device (curve 1) and comparative example be ITO/MoO
3/ NPB/Alq
3the brightness of organic electroluminescence device (curve 2) of/Bphen/LiF/Ag and the relation of luminous efficiency.In organic electroluminescence device prepared by comparative example, each layer thickness is identical with each layer thickness in organic electroluminescence device prepared by embodiment 1.
Can see from Fig. 3, under different brightness, the luminous efficiency of embodiment 1 is all larger than comparative example, the maximum lumen efficiency of embodiment 1 is 9.67lm/W, and comparative example be only 7.25lm/W, and the luminous efficiency of comparative example declines fast along with the increase of brightness, this explanation, patent of the present invention is by preparing the cathode construction of sandwich construction, this cathode construction layer is by sodium salt doped layer, first metal-doped layer and the second metal-doped layer composition, sodium salt material and crystallinity Organic Electron Transport Material form, the work function of sodium salt material close to organic material LUMO relatively, the injection barrier of electronics can be reduced, improve the injection efficiency of electronics, crystalline material makes film surface form wave structure, make the light scattering of Vertical Launch, no longer vertical, thus can not be coupled with the free electron of metal level (parallel free electron can be coupled with vertical photon and lose), improve photon utilance, simultaneously, material has electronic transmission performance, the transmission rate of electronics can be improved, then one deck first metal-doped layer is prepared, be made up of the metal of low-function function and VB race metallic compound composition material, low workfunction metal has lower work function, electronic barrier can be reduced further and improve electron injection efficiency, and can carrier concentration be improved thus improve conductivity, VB race element transmitance in visible-range is higher, finally prepare one deck second metal-doped layer, be made up of high-work-function metal and passivating material, high-work-function metal free electronic concentration is larger, can further improve conductivity, the reflection of light can be improved simultaneously, passivating material effectively can improve the stability of device, starvation and steam enter into device, this composite cathode effectively can improve luminous efficiency.
The luminous efficiency of organic electroluminescence device prepared of each embodiment is all similar with embodiment 1 below, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/MoO
3/ TCTA/ADN/Bphen/CsF/Na
2cO
3: OXD-7/Sr:V
2o
5/ Ag:Al
2o
3organic electroluminescence device.
First AZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is MoO
3, thickness is 80nm; Evaporation hole transmission layer: material is TCTA, thickness is 60nm; Evaporation luminescent layer: selected materials is ADN, thickness is 5nm; Evaporation electron transfer layer, material is Bphen, and thickness is 200nm; Evaporation electron injecting layer, material is CsF, and thickness is 10nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare sodium salt doped layer at described electron injecting layer surface evaporation, material is Na
2cO
3: OXD-7, Na
2cO
3be 15: 1 with OXD-7 mass ratio, thickness is 300nm, then prepares the first metal-doped layer by electron beam evaporation plating, and material is Sr:V
2o
5, Sr and V
2o
5mass ratio be 10: 1, thickness is 10nm, and then being prepared by electron beam evaporation plating mode has the second metal-doped layer, and material is Ag:Al
2o
3, Ag and Al
2o
3mass ratio be 1: 1, thickness is 300nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 2 × 10
-3pa, the energy density of electron beam evaporation plating is 10W/cm
2, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s;
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 2 × 10
-3pa, operating current is 3A, and the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s.
Embodiment 3
Structure prepared by the present embodiment is IZO/WO
3/ TAPC/Alq
3/ TAZ/Cs
2cO
3/ NaF:BCP/Ca:Nb
2o
5the organic electroluminescence device of/Al:NiO/.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is WO
3, thickness is 20nm; Evaporation hole transmission layer: material is TAPC, thickness is 30nm; Evaporation luminescent layer: selected materials is Alq
3, thickness is 40nm; Evaporation electron transfer layer, material is TAZ, and thickness is 60nm; Evaporation electron injecting layer, material is Cs
2cO
3, thickness is 0.5nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare sodium salt doped layer at described electron injecting layer surface evaporation, material is NaF:BCP, NaF and BCP mass ratio is 5: 1, and thickness is 50nm, then prepares the first metal-doped layer by electron beam evaporation plating, and material is Ca:Nb
2o
5, Ca and Nb
2o
5mass ratio be 20: 1, thickness is 50nm, and then being prepared by electron beam evaporation plating mode has the second metal-doped layer, and material is the mass ratio of Al:NiO, Al and NiO is 5: 1, and thickness is 100nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 5 × 10
-5pa, the energy density of electron beam evaporation plating is 100W/cm
2, the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s;
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 5 × 10
-5pa, operating current is 1.5A, and the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s.
Embodiment 4
Structure prepared by the present embodiment is IZO/V
2o
5/ TCTA/DCJTB/Bphen/CsN
3/ NaBr:PO15/Yb:Ta
2o
5the organic electroluminescence device of/Au:CuO.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is V
2o
5, thickness is 30nm; Evaporation hole transmission layer: material is TCTA, thickness is 50nm; Evaporation luminescent layer: selected materials is DCJTB, thickness is 5nm; Evaporation electron transfer layer, material is Bphen, and thickness is 40nm; Evaporation electron injecting layer, material is CsN
3, thickness is 0.5nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare sodium salt doped layer at described electron injecting layer surface evaporation, material is NaBr:PO15, NaBr and PO15 mass ratio is 8: 1, thickness is 150nm, then prepares the first metal-doped layer by electron beam evaporation plating, and material is Yb:Ta
2o
5, Yb and Ta
2o
5mass ratio be 12: 1, thickness is 30nm, and then being prepared by electron beam evaporation plating mode has the second metal-doped layer, and material is the mass ratio of Au:CuO, Au and CuO is 4: 1, and thickness is 250nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 5 × 10
-4pa, the energy density of electron beam evaporation plating is 50W/cm
2, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 5nm/s;
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 5 × 10
-4pa, operating current is 2A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 5nm/s.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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. an organic electroluminescence device, it is characterized in that, comprise the anode stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described cathode layer is by sodium salt doped layer, first metal-doped layer and the second metal-doped layer composition, described sodium salt doped layer comprises sodium salt material and is entrained in the Organic Electron Transport Material in described sodium salt material, described sodium salt material is selected from sodium carbonate, sodium chloride, at least one in sodium fluoride and sodium bromide, described Organic Electron Transport Material HOMO energy level is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, described first metal-doped layer comprises the first metal material and is entrained in the VB race metallic compound in described first metal material, described the first metal layer material work functions is-2.0eV ~-3.5eV, described VB race metallic compound is selected from tantalum pentoxide, at least one in vanadic oxide and niobium pentaoxide, described second metal-doped layer comprises the second metal material and is entrained in the passivating material in described second metal material, described second metal material work function is-4.0eV ~-5.5eV, described passivating material is selected from silicon dioxide, aluminium oxide, at least one in nickel oxide and cupric oxide.
2. organic electroluminescence device according to claim 1, it is characterized in that, described first metal material is selected from least one in magnesium, strontium, calcium and ytterbium, described second metal material is selected from least one in silver, aluminium, platinum and gold, described Organic Electron Transport Material is selected from 1,2,4-triazole derivative, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles], 2,9-dimethyl-4,7-biphenyl-1, at least one in 10-phenanthrolene and 2,8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene.
3. organic electroluminescence device according to claim 1, it is characterized in that, described in described sodium salt doped layer material, the mass ratio of sodium salt material and described Organic Electron Transport Material is 5:1 ~ 15:1, the mass ratio of the first metal material described in described first metal-doped layer and described VB race metallic compound is 10: 1 ~ 20: 1, and the mass ratio of described second metal material and described passivating material is 1: 1 ~ 5: 1.
4. organic electroluminescence device according to claim 1, is characterized in that, described sodium salt doped layer thickness is 5nm ~ 300nm, and described first metal-doped layer thickness is 10nm ~ 50nm, and described second metal-doped layer thickness is 100nm ~ 300nm.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is formed successively at anode surface; And
Sodium salt doped layer is prepared by the method for thermal resistance evaporation on electron injecting layer surface, described sodium salt doped layer comprises sodium salt material and is entrained in the Organic Electron Transport Material in described sodium salt material, described sodium salt material is selected from sodium carbonate, sodium chloride, at least one in sodium fluoride and sodium bromide, described Organic Electron Transport Material HOMO energy level is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, then the first metal-doped layer is prepared on described sodium salt doped layer surface by electron beam evaporation plating mode, described first metal-doped layer comprises the first metal material and is entrained in the VB race metallic compound in described first metal material, described the first metal layer material work functions is-2.0eV ~-3.5eV, described VB race metallic compound is selected from tantalum pentoxide, at least one in vanadic oxide and niobium pentaoxide, described second metal-doped layer is prepared at described first metal-doped layer surface evaporation by the mode of electron beam evaporation plating, described second metal-doped layer comprises the second metal material and is entrained in the passivating material in described second metal material, described second metal material work function is-4.0eV ~-5.5eV, described passivating material is selected from silicon dioxide, aluminium oxide, at least one in nickel oxide and cupric oxide.
6. the preparation method of organic electroluminescence device according to claim 5, it is characterized in that: described first metal material is selected from least one in magnesium, strontium, calcium and ytterbium, described second metal material is selected from least one in silver, aluminium, platinum and gold, described Organic Electron Transport Material is selected from 1,2,4-triazole derivative, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles], 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene and 2, at least one in 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene.
7. the preparation method of organic electroluminescence device according to claim 5, it is characterized in that: described in described sodium salt doped layer material, the mass ratio of sodium salt material and described Organic Electron Transport Material is 5: 1 ~ 15: 1, the mass ratio of the first metal material described in described first metal-doped layer and described VB race metallic compound is 10:1 ~ 20:1, and the mass ratio of described second metal material and described passivating material is 1: 1 ~ 5: 1.
8. the preparation method of organic electroluminescence device according to claim 5, it is characterized in that: described sodium salt doped layer thickness is 5nm ~ 300nm, first metal-doped layer thickness is 10nm ~ 50nm, and described second metal-doped layer thickness is 100nm ~ 300nm.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the concrete technology condition of described thermal resistance evaporation mode is: operating pressure is 2 × 10
-3pa ~ 5 × 10
-5pa, operating current is 1A ~ 3A, and the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
10. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the concrete technology condition of described electron beam evaporation plating mode is: operating pressure is 2 × 10
-3~ 5 × 10
-5pa, the energy density of electron beam evaporation plating is 10W/cm
2~ l00W/cm
2, the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310452689.7A CN104518150A (en) | 2013-09-28 | 2013-09-28 | Organic electroluminescent device and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310452689.7A CN104518150A (en) | 2013-09-28 | 2013-09-28 | Organic electroluminescent device and method for preparing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104518150A true CN104518150A (en) | 2015-04-15 |
Family
ID=52793139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310452689.7A Pending CN104518150A (en) | 2013-09-28 | 2013-09-28 | Organic electroluminescent device and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104518150A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108957895A (en) * | 2018-06-25 | 2018-12-07 | 常州铱视光电科技有限公司 | Acid-base response electrochomeric films, preparation method and application and electrochromic device |
| JP2021057296A (en) * | 2019-10-01 | 2021-04-08 | 株式会社Ｊｏｌｅｄ | Display panel using self-luminous element and method for manufacturing the same |
| CN115332457A (en) * | 2021-05-11 | 2022-11-11 | 广东聚华印刷显示技术有限公司 | Light emitting device and method for manufacturing the same |
-
2013
- 2013-09-28 CN CN201310452689.7A patent/CN104518150A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108957895A (en) * | 2018-06-25 | 2018-12-07 | 常州铱视光电科技有限公司 | Acid-base response electrochomeric films, preparation method and application and electrochromic device |
| CN108957895B (en) * | 2018-06-25 | 2021-06-11 | 常州铱视光电科技有限公司 | Acid-base responsive electrochromic film, preparation method and application thereof, and electrochromic device |
| JP2021057296A (en) * | 2019-10-01 | 2021-04-08 | 株式会社Ｊｏｌｅｄ | Display panel using self-luminous element and method for manufacturing the same |
| JP7423238B2 (en) | 2019-10-01 | 2024-01-29 | ＪＤＩ Ｄｅｓｉｇｎ ａｎｄ Ｄｅｖｅｌｏｐｍｅｎｔ 合同会社 | Display panel using self-luminous elements and manufacturing method thereof |
| CN115332457A (en) * | 2021-05-11 | 2022-11-11 | 广东聚华印刷显示技术有限公司 | Light emitting device and method for manufacturing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104518150A (en) | Organic electroluminescent device and method for preparing same | |
| CN103972420A (en) | Organic light-emitting device and method for manufacturing same | |
| CN104518102A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104518108A (en) | Organic electroluminescent device and method for preparing same | |
| CN104518106A (en) | Organic light-emitting device and making method thereof | |
| CN104518148A (en) | Organic electroluminescent device and method for preparing same | |
| CN104518145A (en) | Organic electroluminescent device and method for preparing same | |
| CN104733635A (en) | Organic light-emitting device and preparation method thereof | |
| CN103972421A (en) | Organic light-emitting device and production method thereof | |
| CN104518147A (en) | Organic electroluminescent device and method for preparing same | |
| CN104659277A (en) | Organic electroluminescence device and preparation method thereof | |
| CN103972408A (en) | Organic light-emitting device and method for manufacturing same | |
| CN104518109A (en) | Organic electroluminescent device and method for preparing same | |
| CN104733639A (en) | Organic light-emitting device and manufacturing method thereof | |
| CN104659273A (en) | Organic electroluminescence device and preparation method thereof | |
| CN104518140A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104518138A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104425745A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104659219A (en) | Organic electroluminescence device and preparation method thereof | |
| CN103972404A (en) | Organic light-emitting device and production method thereof | |
| CN104518100A (en) | Organic electroluminescent device and preparation method thereof | |
| CN103972403A (en) | Organic light-emitting device and production method thereof | |
| CN103972412A (en) | Organic light-emitting device and method for manufacturing same | |
| CN104518152A (en) | Organic electroluminescent device and method for preparing same | |
| CN104638148A (en) | Organic light-emitting device and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150415 |
|
| WD01 | Invention patent application deemed withdrawn after publication |