EP2798682A1 - Transparent anode for an oled - Google Patents
Transparent anode for an oledInfo
- Publication number
- EP2798682A1 EP2798682A1 EP12819119.4A EP12819119A EP2798682A1 EP 2798682 A1 EP2798682 A1 EP 2798682A1 EP 12819119 A EP12819119 A EP 12819119A EP 2798682 A1 EP2798682 A1 EP 2798682A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- silver
- snzno
- layers
- zno
- 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.)
- Withdrawn
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000004332 silver Substances 0.000 claims abstract description 111
- 229910052709 silver Inorganic materials 0.000 claims abstract description 110
- 239000011787 zinc oxide Substances 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 21
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011521 glass Substances 0.000 claims abstract description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 3
- 239000011707 mineral Substances 0.000 claims abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 109
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 56
- 239000010936 titanium Substances 0.000 claims description 49
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000005693 optoelectronics Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims description 4
- 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 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims 1
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 5
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 5
- 239000004411 aluminium Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 353
- 238000000137 annealing Methods 0.000 description 22
- 239000011701 zinc Substances 0.000 description 22
- 210000001787 dendrite Anatomy 0.000 description 20
- 230000003287 optical effect Effects 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000011241 protective layer Substances 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 9
- -1 Nb 2 O 5 ) Chemical compound 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 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 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 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 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910005535 GaOx Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- ODNHQUQWHMGWGT-UHFFFAOYSA-N iridium;oxotin Chemical compound [Ir].[Sn]=O ODNHQUQWHMGWGT-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/816—Multilayers, e.g. transparent multilayers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3639—Multilayers containing at least two functional metal layers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3652—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
- C03C17/3671—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electrodes
-
- 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
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
- C03C2217/948—Layers comprising indium tin oxide [ITO]
Definitions
- the present invention relates to a transparent, supported electrode comprising a stack of thin layers of silver and metal oxides, an OLED device containing at least one such electrode, preferably as an electroluminescent optoelectronic device. anode, and a method of manufacturing such a device.
- Transparent conductive oxides and in particular ⁇ (iridium tin oxide) are widely known and used as transparent material to form thin transparent electrodes for electronic devices and in particular optoelectronic devices.
- OLEDs organic light emitting diodes
- ⁇ is used as anode material because it is characterized by a high output work, generally between 4.5 and 5, 1 eV.
- the square resistance (RD) of ⁇ is too high and, in order to obtain a good homogeneity of light emission, it is necessary to double the ITO layer of one or more thin conducting layers. , such as silver layers.
- a good crystallinity of the silver layer it is in a known manner deposited on a crystalline sublayer of zinc oxide (ZnO), generally doped with aluminum (AZO).
- ZnO zinc oxide
- AZO aluminum
- This crystalline sub-layer of ZnO or of AZO is deposited, in turn, on a relatively more amorphous tin-zinc mixed oxide layer (SnZnO) which makes it possible to limit the RM S roughness of the following layers to a given value. generally less than 1 nm.
- each silver layer is generally covered with a thin metal layer, called a “blocker” or “on-blocker”, typically 0.5 to 5 nm, intended to protect the silver against oxidation during the stage of deposit of the next layer.
- a blocker typically 0.5 to 5 nm
- These layers of protection are sometimes also called sacrificial layers because they are consumed by reacting with the oxygen against which they must protect the underlying layer of silver.
- Processes for manufacturing optoelectronic devices containing electrodes with such stacks of silver layers generally comprise at least one step of heating at high temperature (150 ° C - 350 ° C) for the purpose of etching, cleaning or of the passivation of the electrode.
- the Applicant has found that the optical and electrical properties of the silver stacks are modified by this annealing step, often unavoidable. While moderate temperature annealing certainly enhances the crystallinity of the silver layers and therefore the square resistance and electrode absorption, the Applicant has observed that, unfortunately, at higher annealing temperatures, typically Above 200 ° C, there was an increase in square resistance and absorption (decrease in light transmission).
- dendrites undesirable surface imperfections
- the Applicant has also observed the appearance, during annealing, of undesirable surface imperfections, hereinafter referred to as "dendrites".
- the dendrites are local depletions of silver which create, on the surface of the electrode, depressions of a depth of about 5 to 10 nm and a diameter ranging from about ten nanometers to about ten about micrometers. In the center of such a "well", one often observes a projecting part.
- This local increase in roughness may result in an increase in short-circuit currents.
- FIG. 2 is a scanning electron micrograph (SEM) of dendrites observed after a one-hour annealing at 300 ° C. of a stack of thin layers, with two silver layers, according to the state of the art shown in Figure 1.
- SEM scanning electron micrograph
- the present invention is based on the idea of protecting the silver layer or layers by the insertion of a protective layer, which is supposed to function as an oxygen barrier, between the silver layer and the SnZnO layer (s) of the stack.
- This insertion must of course not be made between the silver layer and the crystalline layer of ZnO (AZO) directly underlying which is essential for good crystal growth during the deposition of the silver layer.
- the Applicant has discovered that silicon nitride (Si 3 N 4 ) and silica (SiO 2 ), even in thin thickness, make it possible to play this protective role and effectively reduce, or even eliminate, the formation of dendrites without their presence does not result in a degradation of the electrical and optical properties of the electrode before and after annealing. As will be shown hereinafter in the example, it was further observed that the presence of Si 3 N 4 or SiO 2 resulted in an interesting decrease in square resistance and absorption.
- the present invention therefore relates to a transparent electrode for organic light-emitting diode (OLED), comprising, on a transparent mineral glass support, n unit stacks of thin layers, each unit stack comprising successively, starting from the glass support,
- OLED organic light-emitting diode
- a mixed tin-zinc oxide layer (called SnZnO, more precisely Sn x Zn y O), preferably at least 15 nm thick and even at least 25 nm thick, optionally doped
- a crystalline layer of zinc oxide called ZnO
- ZnO zinc oxide
- AZO aluminum
- GZO, AGZO gallium
- the electrode being characterized in that between each layer of silver and the SnZnO layer or layers closest thereto is disposed (d) a layer of silicon nitride (called Si 3 N 4 ) or in silica (called SiO 2 ), optionally doped with a metal.
- Si 3 N 4 silicon nitride
- SiO 2 silica
- the layer (a) is preferably a substantially amorphous layer of SnZnO.
- the ratio of the number of atoms of Sn to the number of Zn atoms is preferably between 20/80 and 80/20, in particular between 30/70 and 70/30.
- the total weight percentage of Sn metal is preferably from 20 to 90% (and preferably from 80 to 10% for Zn) and in particular from 30 to 80% (and preferably from 70 to 20% for Zn).
- the weight ratio Sn / (Sn + Zn) is preferably from 20 to 90% and in particular from 30 to 80%.
- the sum of the percentages by weight of Sn + Zn is at least 90% by total weight of metal, more preferably at least 95% preferably and even at least 97%. It is further preferred that it be devoid of indium or at least a percentage of indium by total metal weight of less than 10% or even 5%. It is preferred that the layer (a) consists essentially of tin oxide and zinc.
- a metal zinc and tin target whose weight percentage (total target) of Sn is preferably from 20 to 90 (and preferably from 80 to 10 for Zn) and in particular from 30 to 80 for Sn (and preferably 80 to 30 for Zn) in particular, the ratio Sn / (Sn + Zn) is preferably from 20 to 90% and in particular from 30 to 80% and / or the sum of percentages by weight of Sn + Zn of at least 90%, more preferably at least 90% and even at least 95%, or even at least 97%.
- the metal zinc and tin target can be doped with a metal preferentially with antimony (Sb).
- the role of the layer (a) is to smooth, that is to say to limit the roughness of the thin layers (AZO and Ag, or GZO and Ag preferably) deposited thereafter. It can be doped with a metal, for example with antimony (Sb).
- OLED electrode used in the present application implies, inter alia, that the present invention does not encompass similar multilayer structures whose last layer (the outermost layer) is a nonconductive layer, such as a silicon carbide layer, or preferably at least one non-conductive layer sufficiently thick to prevent vertical conduction of silver to the organic electroluminescent layer. Indeed such structures would be inappropriate for use as an electrode.
- the SnZnO layer is said (a) or a)
- the ZnO layer is said (b) or b)
- the Ag layer is said (c) or c)
- the Si 3 N 4 layer or Si0 2 is said (d) or d) indifferently.
- the electrode of the present invention preferably comprises from 1 to 4 unit stacks with a silver layer, that is to say n is preferably an integer between 1 and 4, in particular between 2 and 3, and is particularly worth 2.
- the expression between a terminal A and a terminal B includes the terminals A and B.
- These silver layers preferably have a thickness of between 4 nm and 30 nm, in particular between 5 and 25 nm and particularly preferably between 6 and 12 nm.
- the total thickness of the electrode is less than 300 nm and even 250 nm.
- a thin layer is a layer of thickness less than 150 nm.
- the protective layer is preferably a layer of Si 3 N 4 or SiO 2 "doped", for example aluminum or zirconium.
- the silicon nitride is deposited by reactive cathodic sputtering from a metal target (Si) using nitrogen as a reactive gas.
- the silica is deposited by reactive cathodic sputtering from a metal target (Si) using oxygen as a reactive gas.
- a metal target Si
- oxygen as a reactive gas.
- Aluminum and / or zirconium are present in the target (Si) in relatively large amounts, generally ranging from a few percent (at least 1%) to more than 10%, typically up to 20%, going beyond conventional doping, intended to give the target sufficient conductivity.
- an aluminum-doped silicon nitride layer (in particular the dendrite barrier layer) preferably comprises a percentage by weight of aluminum relative to the weight percentage of silicon and aluminum, hence Al / ( If + AI), ranging from 5% to 15%.
- Aluminum doped silicon nitride corresponds more exactly to a silicon nitride comprising aluminum (SiAIN).
- a layer of aluminum nitride doped with aluminum or even zirconium in particular the dendrite barrier layer
- the sum of the percentages by weight of Si + Al or Si + Zr + Al is from less than 90% by total weight of metal, or even preferably 95% by weight or even at least 99%.
- a layer of aluminum nitride doped with aluminum and zirconium corresponds more exactly to a silicon and zirconium nitride comprising aluminum.
- the weight percentage of zirconium in the layer may be from 10 to 25% by total weight of metal.
- the aluminum doped silicon oxide (dendrite barrier) layer preferably comprises a percentage by weight of aluminum relative to the weight percentage of silicon and aluminum, hence Al / (Si + AI), ranging from 5% to 15%.
- Silicon oxide doped with aluminum corresponds more exactly to a silicon oxide comprising aluminum.
- the sum of the percentages by weight of Si + Al or Si + Zr + Al is at least 90% by total weight of metal preferably at least 95% or even at least 99%.
- silica and silicon nitride have proved to be effective protective layers, even at low thickness.
- the thickness needed to reduce or prevent the formation of dendrites increases with temperature and annealing time. For annealing temperatures below 450 ° C. and annealing times of less than 1 hour, layer thicknesses below 15 nm appear to be sufficient.
- the thickness of the Si 3 N 4 or SiO 2 layer is preferably between 1 and 10 nm, in particular between 2 and 9 nm, and in particular preferred between 3 and 8 nm.
- Each silver layer of a unitary stack according to the invention is protected by the layer of Si 3 N 4 or SiO 2 not only against the SnZnO layer below, but also against the SnZnO layer of the next possible stacking unit by a layer of Si 3 N 4 or SiO 2 .
- each silver layer of the electrode according to the invention is protected by a layer of Si 3 N 4 or SiO 2 in particular having a thickness of between 1 and 10 nm, preferably between 2 and 9 nm, in particularly between 3 and 8 nm against a layer SnZnO below, layer of Si 3 N 4 or SiO 2 possibly in contact with the silver layer and also against a SnZnO layer above by a layer of Si 3 N 4 or SiO 2 in particular with a thickness of between 1 and 10 nm, preferably between 2 and 9 nm, in particular between 3 and 8 nm.
- At least one of the stackings of layers further comprises, above the metal silver layer, generally in contact therewith, a sacrificial layer comprising a metal chosen from titanium, nickel, chromium, niobium or a mixture thereof.
- a sacrificial layer comprising a metal chosen from titanium, nickel, chromium, niobium or a mixture thereof.
- blockers or overblockers is known and is mainly used to protect the silver layer against possible chemical or thermal degradation during the manufacturing process of the invention.
- 'electrode These layers can be partially oxidized. They are preferably very thin (generally less than 3 nm, for example of the order of 1 nm), so as not to affect the light transmission of the stack.
- Titanium (Ti, TiO x ), which protects the silver layer (s) during the manufacturing process steps of the OLED and absorbs little in particular after heat treatment, is particularly preferred.
- the electrode may comprise at least two metallic silver layers (preferably two) and only above the last layer of metallic silver, preferably in contact therewith, is a sacrificial layer comprising a chosen metal among titanium, nickel, chromium, niobium or a mixture thereof.
- a single surblocker preferably titanium, on the second layer of silver can sometimes be enough to protect the silver layers during the steps of manufacturing processes OLED.
- each unit stack comprises only one layer of SnZnO.
- n 2 or more, between two silver layers, there are only two layers of SiO 2 or Si 3 N 4 .
- the ZnO layer (under the silver layer) may preferably be doped zinc oxide, preferably Al (AZO), Ga (GZO) as already indicated, even by B, Se, or Sb, or by Y, F, V, Si, Ge, Ti, Zr, Hf and even by In to facilitate the deposition and a lower electrical resistivity.
- AZO Al
- GZO Ga
- Y Y
- Zn a Sn b O zinc-containing crystalline layer containing a very small amount of tin which can be likened to doping, called Zn a Sn b O, preferably with the weight ratio following Zn / (Zn + Sn).
- these crystalline layers are preferably amorphous layers for better crystallization of silver.
- This layer of Si 3 N 4 is preferably between 1 and 15 nm, in particular between 2 and 9 nm, and particularly preferably between 3 and 8 nm. Its thickness can be adjusted according to optical criteria as well. It may be thicker than in the case of a unitary stack according to the invention.
- the outermost layer ie the layer in contact with the hole transport layer (HTL)
- HTL hole transport layer
- Some transparent conductive oxides are known for their relatively high output work. ITO, for example, has an output work that is typically greater than 4.5 eV, sometimes greater than 5 eV.
- the electrode according to the invention therefore comprises above the last layer of silver (in particular ri m stacking) - which is generally a silver layer or a blocking layer - a layer of a transparent conductive oxide (TCO), preferably a layer of ITO (indium oxide doped with tin).
- TCO transparent conductive oxide
- This layer described as an adaptation layer of the output work, can also be the penultimate layer of the electrode (the anode), the last layer then being a layer thin enough not to disturb the adaptation function. of the penultimate exit work and to preserve the vertical conductivity of the silver towards the layer containing an organic electroluminescent substance.
- This TCO layer preferably has a thickness of between 5 and 100 nm, in particular between 10 and 80 nm and particularly preferably between 10 and 50 nm.
- This layer of TCO is preferably directly on the (only) onblocker of the last layer of silver - preferably titanium surbloqueur-.
- this TCO layer is at least one of the following metal oxides, optionally doped: indium oxide, zinc oxide, optionally sub-stoichiometric, molybdenum oxide (MoO 3 ), tungsten oxide ( WO 3 ), vanadium oxide (V 2 O 5 ), indium tin oxide (ITO), indium zinc oxide (IZO or even IAZO or IGZO).
- ITO, MoO 3 , WO 3 , V 2 0 5 are preferred as the last, and even the only layer above the overblocker.
- a range of preferred proportions for ⁇ is 85 to 92% by weight of In 2 0 3 and 8 to 15% by weight of SnO 2 .
- the protective layer (d) located between the silver layer and the SnZnO layer or layers in the vicinity, must not be inserted between the silver layer (c) and the underlying crystal layer ZnO (b).
- the layer disposed between each silver layer and each of the SnZnO layers closest to the silver layer is a silica layer (Si0 2 ).
- Each unitary stack is composed of, or consists of, the succession (preferably strict) of the following layers:
- a layer of Si 3 N 4 is also under each SnZnO arranged between two silver layers, preferably directly below SnZnO.
- the thickness of this Si 3 N 4 layer is preferably between 1 and 10 nm, in particular between 2 and 9 nm, and particularly preferably between 3 and 8 nm.
- a layer of Si 3 N 4 is chosen for all the protective layers.
- the layer between each silver layer and each of the SnZnO layers closest to said silver layer is a silica (SiO 2 ) layer.
- Each unit stack consists of, or consists of, the succession (preferably strict) of the following layers:
- layer (e) Ti is a "blocker” type layer preferably of titanium.
- an Si0 2 layer is also under each SnZnO arranged between two silver layers, preferably directly below SnZnO.
- the thickness of this layer of SiO 2 is preferably between 1 and 10 nm, in particular between 2 and 9 nm, and particularly preferably between 3 and 8 nm.
- a layer of Si0 2 is chosen for all the protective layers.
- SnZnO / SiO 2 or Si 3 N 4 / ZnO / Ag / SiO 2 or Si 3 N 4 / SnZnO / SiO 2 or Si 3 N 4 / ZnO / Ag / sacrificial layer preferably Ti.
- an electrode with two layers of metallic silver comprising in this order a first layer of silver, a layer Si0 2 or Si 3 N 4 (as the layer d) preferably) and unit stack comprising the layers a) / d) / b) / c), c) which corresponds to the second and preferably the last layer of metallic silver, at least 60%, preferably at least 80%, of the the thickness of the layers separating the two silver layers is formed of the thickness of the layer a) and / or its thickness is preferably greater than or equal to 50 nm, and better still greater than or equal to 60 nm and preferably less than or equal to 100 nm .
- two unit stacks (the last layer is preferably a layer of metallic silver or a sacrificial layer, of the onblocker type) can be separated by the layer Si0 2 or Si 3 N 4 and by one or more other layers, and preferably by a single other layer than the Si0 2 or Si 3 N 4 layer, for example ZnO or AZO or GZO.
- a crystalline ZnO (or AZO or GZO) layer separates the last layer of a stack (which is preferably a layer of metallic silver or a sacrificial layer, of the overblocker type) from the first layer of the next stack.
- the (first) protective layer Si0 2 or Si 3 N 4 (as the layer d) preferably) is then inserted between this layer of ZnO (or AZO or GZO) and the SnZnO layer (layer (a)) of the next unit stack.
- This layer of ZnO on the silver layer may preferably be doped zinc oxide, preferably Al (AZO), Ga (GZO), or even B, Se, or Sb, or else Y, F, V , Si, Ge, Ti, Zr, Hf and even In to facilitate deposition and a lower electrical resistivity.
- AZO Al
- GZO Ga
- B, Se or Sb
- Y, F, V , Si, Ge, Ti, Zr, Hf and even In to facilitate deposition and a lower electrical resistivity.
- its thickness is less than 30 nm, more preferably less than 15 nm, more preferably less than or equal to 10 nm.
- each SiO 2 or Si 3 N 4 protective layer is contact, on one side, with a layer of ZnO, preferably doped with aluminum, and on the other side with a layer of SnZnO.
- the electrode of the present invention comprises at least two single stacks of thin layers as described above, it comprises preferably between the last layer of a stack (which is preferably a layer of metallic silver or a sacrificial layer, of the overblocking type) and the first layer of the next stack, successively
- a layer of ZnO, preferably doped with aluminum preferably having a thickness of less than 20 nm, even at 10 nm and
- a layer of Si0 2 or Si 3 N 4 (in addition to the layer d) and similar to the layer d), preferably of thickness between 1 and 10 nm, preferably between 2 and 9 nm in particular between 3 and 8 nm, preferably in contact with the ZnO layer.
- the metallic silver layer may be pure, alloyed, or doped, for example with Pd, Cu, Sb ...
- the electrode comprises, from the glass, the following sequence (preferably strict): (p layer (s)) / a) / d) / b) / c) / (q layer ( s)) / Si0 2 or Si 3 N 4 / a) / d) / b) / c) layer and preferably p is an integer preferably less than or equal to 2, more preferably 1 or even 0 and q is an integer less than 3.
- the layer or layers added preferably: have an optical index (average) at 550 nm greater than equal to 1.7, even at 1.8 and / or,
- oxides such as niobium oxide (such as Nb 2 O 5 ), zirconium oxide (such as Zr0 2 ), alumina (such as Al 2 O 3 ), tantalum oxide (such as Ta 2 O 5 ), tin oxide (such as SnO 2 )), or silicon nitride (such as Si 3 N 4 ) .
- niobium oxide such as Nb 2 O 5
- zirconium oxide such as Zr0 2
- alumina such as Al 2 O 3
- tantalum oxide such as Ta 2 O 5
- tin oxide such as SnO 2
- silicon nitride such as Si 3 N 4
- the thickness is preferably less than 10 nm.
- the thickness is preferably greater than 20 nm, preferably 30 to 50 nm.
- the thickness is preferably greater than 40 nm, preferably 60 to 100nm, or even 60 to 90nm.
- L 1 may be chosen to be greater than 20 nm, better still greater than or equal to 40 nm, and less than 180 nm and even more preferably from 100 nm to 120 nm,
- L2 may be chosen to be greater than 80 nm, better than or equal to 100 nm and less than 280 nm and even better 140nm to 240nm and even 140 to 220nm.
- the thickness is therefore preferably greater than 40 nm, preferably 60 to 100 nm, or even 60 to 90 nm.
- TiN Ti / layer preferably ITO, Mo0 3 , WO 3 , V 2 0 5 , or even AZO, optionally topped with a layer (TiN %) not more than 5nm, better not more than 3nm or 2nm
- 3 N 4 / GZO / Ag / sacrificial layer preferably Ti / layer preferably ITO, Mo0 3 , WO 3 , V 2 0 5 or AZO, possibly topped with a layer (TiN %) of at most 5nm, better of at most 3nm or 2nm.
- 3 N 4 / AZO / Ag / sacrificial layer preferably Ti / layer preferably ITO, Mo0 3 , WO 3 , V 2 0 5 or AZO, optionally topped with a layer (TiN %) of at most 5nm, better not more than 3nm or 2nm
- -SnZnO / SiO 2 or Si 3 N 4 / GZO / Ag / (Ti /) SiO 2 or Si 3 N 4 / SnZnO / SiO 2 or Si 3 N 4 / GZO / Ag / sacrificial layer preferably Ti / layer preferably ITO, Mo0 3 , W0 3 , V 2 0 5 or AZO, possibly surmounted by a layer (TiN %) of at most 5nm, better not more than 3nm or 2nm.
- each onblocker titanium or NiCr, etc.
- the electrode according to the invention can form a bilayer (preferably) or a tri-layer with silver, thus comprises at least two layers of metallic silver, and for example n is equal to 1 and the unitary stack comprises a protection layer Si0 2 or Si 3 N 4 / a) / d) / b) / c) which is located above (preferably directly or on an overblocking sacrificial layer or even on a layer of ZnO) with a protective layer silver which first layer of silver starting from the glass support, and preferably under the first layer of silver is arranged a multilayer selected from the following:
- a multilayer which comprises a layer of SnZnO (of composition as already described for b)), preferably at least 20 nm, followed by a layer of silicon nitride Si 3 N 4 (as already described for d)) directly under the first layer of silver, in particular multilayer of thicknesses adjusted for optics,
- a multilayer which comprises a layer of silicon nitride Si 3 N 4 (of composition as already described for d)), for example at least 20 nm or even at least 35 nm or 40 nm, followed by a layer of ZnO (doped), (as already described for b)), in particular multilayer of thicknesses adjusted for optics,
- a multilayer which preferably comprises in this order:
- a first oxide layer preferably Ti0 2 (20 to 50 nm preferably) or niobium oxide (such as Nb 2 0 5 to 20 preferably 50 nm), even the oxide layers already above as zirconium oxide (such as ZrO 2 ), alumina (such as Al 2 O 3 ), tantalum oxide (such as Ta 2 O 5 ), tin oxide (such as SnO 2 ),
- a layer (thin) of silicon nitride or silica which is also capable of forming a barrier to dendrites, such as that already described for d) for the unitary stack, preferably of thickness between 1 and 10 nm, of preferably between 2 and 9 nm, in particular between 3 and 8 nm a ZnO layer as already described for b) (AZO, GZO ...), preferably less than 10 nm thick.
- the first layer or layers added preferably:
- optical index (average) at 550 nm greater than equal to 1.7, even at 1.8 and / or
- n 1, some examples of particularly preferred stacks are given below (with optional doping not reprecised for the layers other than the layers under silver):
- Ti / (AZO or GZO /) SiO 2 or Si 3 N 4 / SnZnO / SiO 2 or Si 3 N 4 / AZO or GZO / Ag / sacrificial layer preferably Ti preferably ITO, M0O 3 , WO 3 , V 2 O 5 , or even AZO, optionally topped with a layer (TiN 2) of at most 5 nm, better at most 3 nm or 2 nm
- -SnZnO (of at least 20 nm, better still at least 30 nm) / Si 3 N 4 / Ag / (Ti / (AZO or GZO /) SiO 2 or Si 3 N 4 / SnZnO / SiO 2 or Si 3 N 4 / AZO or GZO / Ag / sacrificial layer preferably Ti / layer preferably ITO, Mo0 3 , WO 3 , V 2 0 5 or AZO, optionally topped with a layer (TiN %) of at most 5nm, better not more than 3nm or 2nm
- oxide layer preferably TiO 2 / SiO 2 or Si 3 N 4 / AZO or GZO / Ag / (Ti / AZO or GZO /) SiO 2 or Si 3 N 4 / SnZnO / SiO 2 or Si 3 N 4 / ZnO (doped) / Ag / Ti sacrificial layer / layer preferably ITO, Mo0 3 , WO 3 , V 2 0 5 or AZO, optionally topped with a layer (TiN %) of at most 5nm, better d at most 3nm or 2nm.
- the electrode may preferably be directly on the support or on a layer for example of light extraction, in particular a layer of higher refractive index than the support, and / or a diffusing layer.
- the glass may comprise an external light extraction element on the opposite face to the face with the anode) already known per se such that: adding a film (self-supporting) or depositing a diffusing layer for a volume diffusion,
- the electrode according to the invention can alternatively form a bilayer (preferably) or a tri-layer with silver, thus comprises at least two layers of metallic silver, and n is equal to 1 and the unitary stack comprises SnZnO / Si0 2 or Si 3 N 4 / ZnO / Ag where Ag is the first silver layer from the glass support.
- first layer of silver and the second layer of silver it comprises the following multilayer: sacrificial layer preferably Ti / ZnO layer (of composition as already described for b), tq AZO and GZO) with a thickness of preferably adjusted for optics for example at least 50 nm and even between 60 and 110 nm, or 60 to 100 nm.
- the present invention further relates to an optoelectronic device with organic light-emitting diode (OLED) comprising at least one electrode according to the present invention as described above.
- OLED organic light-emitting diode
- This electrode preferably plays the role of anode.
- OLED then includes
- the OLED device may comprise a more or less thick OLED system, for example between 50 and 350 nm
- the electrode is suitable for tandem OLEDs, for example described in the publication entitled “Stacked white organic light-emitting devices based on a combination of fluorescent and phosphorent emitter” by H Kanno et al, applied phys lett 89 023503 (2006)
- the electrode is suitable for OLED devices having a highly doped "HTL" (Hole Transport Layer) layer as described in US7274141 for which the high output work of the last layer of the overlay is immaterial.
- HTL Hole Transport Layer
- the present invention further relates to a method of manufacturing an optoelectronic device according to the invention. This process of course includes the deposition of the successive layers constituting the unit stack or stackings described above.
- the deposition of all these layers is preferably by magnetron sputtering.
- a plasma is created under a high vacuum in the vicinity of a metal or ceramic target comprising the chemical elements to be deposited.
- the cationic active species of the plasma are attracted to the target (cathode) and collide with it. They then communicate their momentum, thereby sputtering the target's atoms in the form of neutral particles that condense on the substrate to form desired thin layers.
- This process is called “reactive" when the thin film formed consists of a material resulting from a chemical reaction between the elements torn off from the target, for example the atoms of a metal target, and the gas contained in the plasma, for example oxygen or nitrogen. It is said to be “nonreactive" when the target has essentially the same chemical composition as the layer formed, for example when it is a ceramic target containing the metal in the form of oxide or nitride. When the deposition is by magnetron sputtering from a ceramic target, the latter is generally doped with at least one metal, for example aluminum, intended to impart sufficient conductivity to the target.
- the method according to the invention further comprises a step of heating the transparent electrode at a temperature greater than 180 ° C., preferably greater than 200 ° C., in particular between 250 ° C. and 450 ° C., and ideally between 300 and 350 ° C, for a duration preferably between 5 minutes and 120 minutes, in particular between 15 and 90 minutes.
- the electrodes of the present invention are distinguished by the absence of dendrite formation at the silver layer and by a remarkable improvement of electrical and optical properties, such as it will be shown below with the help of the application example.
- a transparent electrode according to the state of the art is prepared by magnetron sputtering firstly comprising two single stacks of thin silver layers on a glass support (comparative El), and on the other hand, a transparent electrode according to the invention (E2) which differs from the comparative electrode E1 in that it comprises three thin layers of silicon nitride with a thickness of 4 nm, separating each of the two silver layers of SnZnO layers.
- the layer of Si 3 N 4 : Al is deposited by reactive sputtering using an aluminum doped silicon metal target, in an argon / nitrogen atmosphere,
- each layer of SnZnO is deposited by reactive sputtering using a metal target of zinc and tin in an argon / oxygen atmosphere,
- each AZO layer is deposited by sputtering with a ceramic target of zinc oxide and alumina in an argon / oxygen atmosphere, with a low oxygen content,
- each layer of silver is deposited using a silver target, in a pure argon atmosphere,
- each layer of Ti is deposited using a titanium target, in a pure argon atmosphere,
- the ITO overlay is deposited using a ceramic target of indium oxide and tin oxide in an argon atmosphere enriched with a small amount of oxygen, so as to render it not very absorbent, ⁇ preferably becoming on stoichiometric oxygen.
- the first Ti overblocking layer can be partially oxidized after AZO deposition on top.
- the second Ti overblocking layer may be partially oxidized after ITO deposition over it. Table A below summarizes the deposition conditions as well as the refractive indices:
- a metal target of zinc and antimony-doped tin containing, for example, 65% of Sn, 34% of Zn and 1% of Sb, or comprising 50% by weight Sn, 49% by weight.
- Zn and 1% Sb Table 1 below shows in comparison the chemical composition and the thickness of all the layers forming these two electrodes. Table 1 - Chemical Composition and Layer Thickness
- the electrodes E1 and E2 are heated for 1 hour at a temperature of 300 ° C (annealing).
- the light transmission (TL) and the absorption (Abs) and the resistance (RD) of each of the electrodes are measured before and after this annealing.
- Table 2 shows the results of these measurements, before and after annealing, for the electrode E2 according to the invention in comparison with the electrode El according to the state of the art.
- the annealing results in a degradation of the properties of the comparative electrode E1, that is to say to a decrease in light transmission and to an increase in absorption and resistance per square, while the electrode E2 according to the invention sees these same properties improved (increase of TL and decrease of Abs and RD).
- FIGS. 3a and 3b show the optical microscopy images respectively of the electrode E1 (according to the state of the art) and of the electrode E2 (according to the invention) after annealing at 300.degree. While we see on the first image (El) of many white dots corresponding to the dendrites, these points are completely absent on the second image of the electrode according to the invention (E2).
- a transparent electrode according to the state of the art is prepared by sputtering magnetron sputtering on the one hand, comprising two single stacks of thin silver layers on a glass support (comparative E '), and on the other hand, a transparent electrode according to the invention ( ⁇ 2 ') which is distinguished from the comparative electrode El' in that it comprises three thin layers of silica with a thickness of 5 nm, separating each of the two layers of silver SnZnO layers.
- Table l shows in comparison the chemical composition and the thickness of all the layers forming these two electrodes.
- Electrodes El 'and E2' are heated for 1 hour at a temperature of 300 ° C (annealing).
- the light transmission (TL) and the absorption (Abs) and the resistance (RD) of each of the electrodes are measured before and after this annealing.
- Table 2 shows the results of these measurements, before and after annealing, for the electrode E2' according to the invention in comparison with the electrode El 'according to the state of the art.
- the annealing results in a degradation of the properties of the comparative electrode El ', that is to say to a decrease in the light transmission and to an increase of the absorption and the resistance per square, while the electrode E2 'according to the invention sees these same properties improved (increase of TL and decrease of Abs and RD).
- the layer of SnZnO between the two layers of silver is useful for the resistance to the chemical treatments of the OLED which are the cleaning notably according to the following procedure:
- the detergent is "TFDO W”, sold by Franklab SA. It is organic, non-foaming, with ionic and nonionic surfactants, chelating agents and stabilizers.
- the pH is about 6.8 to 3% dilution.
- the aluminum doped silicon nitride barrier layer may also be replaced by a silicon nitride and SiZrN: Al zirconium layer for example made under a reactive atmosphere from a metal target in the total weight percentages of the following target: Si 76% by weight, Zr 17% by weight, and Al 7% by weight.
- SnZnO / Si 3 N 4 Al / Ag / AZO / Si 3 N 4 : Al / SnZnO / Si 3 N 4 : Al / AZO / Ag / Sacrificial Ti / ITO layer
- SnZnO / Si 3 N 4 AI / AZO / Ag / Si 3 N 4 : Al / SnZnO / Si 3 N 4 : Al / AZO / Ag / Ti / ITO sacrificial layer
- the AZO of the first layer and / or the second layer and / or the layer on the first layer of silver can be replaced (preferably for all these layers) by GZO for example made from a ceramic target for example with 98% by weight of Zn oxide and 2% by weight of GaOx.
- An electrode was made by replacing the first sub layer of SnZnO in E2 with a layer of titanium oxide (which could also be reduced in thickness due to its larger optical index).
- the TiO 2 layer is deposited by sputtering with a titanium oxide ceramic target in an argon atmosphere with oxygen.
- the deposit conditions are collated in the following Table B:
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FR1162472A FR2985091B1 (en) | 2011-12-27 | 2011-12-27 | TRANSPARENT ANODE FOR OLED |
FR1252238A FR2985092B1 (en) | 2011-12-27 | 2012-03-13 | TRANSPARENT ANODE FOR OLED |
PCT/FR2012/053093 WO2013098532A1 (en) | 2011-12-27 | 2012-12-27 | Transparent anode for an oled |
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BE1020676A3 (en) * | 2012-05-08 | 2014-03-04 | Agc Glass Europe | ORGANIC PHOTONIC DEVICE |
FR3015116B1 (en) | 2013-12-17 | 2016-01-01 | Saint Gobain | LIGHT EXTRACTOR SUPPORT AND OLED DEVICE INCORPORATING SAME. |
FR3019941A1 (en) | 2014-04-09 | 2015-10-16 | Saint Gobain | LIGHT EXTRACTING BRACKET AND OLED DEVICE INCORPORATING SAME |
WO2016092902A1 (en) * | 2014-12-09 | 2016-06-16 | リンテック株式会社 | Transparent conductive film and method for producing transparent conductive film |
CN105810842B (en) * | 2014-12-29 | 2019-01-11 | 昆山国显光电有限公司 | The anode construction of Organic Light Emitting Diode |
TWI565116B (en) * | 2015-01-12 | 2017-01-01 | Organic light emitting diode structure | |
JP6586738B2 (en) * | 2015-02-26 | 2019-10-09 | コニカミノルタ株式会社 | Transparent conductive member and method for manufacturing transparent conductive member |
CN105355798A (en) * | 2015-11-25 | 2016-02-24 | 京东方科技集团股份有限公司 | Organic electroluminescent device, manufacturing method thereof, and display device |
CN107010844A (en) * | 2016-12-26 | 2017-08-04 | 武汉长利新材料科技有限公司 | High-performance temperable double-silver LOW-E glass and manufacturing method thereof |
US20190043640A1 (en) * | 2017-08-04 | 2019-02-07 | Vitro Flat Glass, LLC | Protective Layer Over a Functional Coating |
CN111559875B (en) * | 2020-06-19 | 2024-05-14 | 广东旗滨节能玻璃有限公司 | Coated glass and preparation method thereof |
CN113346032B (en) * | 2021-06-01 | 2023-04-07 | 固安翌光科技有限公司 | Organic electroluminescent device |
FR3140955A1 (en) * | 2022-10-13 | 2024-04-19 | Saint-Gobain Glass France | ELECTROCHROMIC GLAZING |
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CA2424746C (en) * | 2000-09-29 | 2011-03-29 | Nippon Sheet Glass Co., Ltd. | Transparent laminate having low emissivity |
DE10135513B4 (en) | 2001-07-20 | 2005-02-24 | Novaled Gmbh | Light-emitting component with organic layers |
JP5261397B2 (en) * | 2006-11-17 | 2013-08-14 | サン−ゴバン グラス フランス | Electrode for organic light emitting device, acid etching thereof, and organic light emitting device incorporating the same |
FR2911130B1 (en) * | 2007-01-05 | 2009-11-27 | Saint Gobain | THIN FILM DEPOSITION METHOD AND PRODUCT OBTAINED |
FR2925981B1 (en) * | 2007-12-27 | 2010-02-19 | Saint Gobain | CARRIER SUBSTRATE OF AN ELECTRODE, ORGANIC ELECTROLUMINESCENT DEVICE INCORPORATING IT. |
FR2939563B1 (en) * | 2008-12-04 | 2010-11-19 | Saint Gobain | PHOTOVOLTAIC PANEL FRONT PANEL SUBSTRATE, PHOTOVOLTAIC PANEL, AND USE OF SUBSTRATE FOR FRONT PANEL VIEW OF PHOTOVOLTAIC PANEL |
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2011
- 2011-12-27 FR FR1162472A patent/FR2985091B1/en not_active Expired - Fee Related
-
2012
- 2012-03-13 FR FR1252238A patent/FR2985092B1/en not_active Expired - Fee Related
- 2012-12-27 EP EP12819119.4A patent/EP2798682A1/en not_active Withdrawn
- 2012-12-27 US US14/367,688 patent/US20140332795A1/en not_active Abandoned
- 2012-12-27 WO PCT/FR2012/053093 patent/WO2013098532A1/en active Application Filing
- 2012-12-27 CN CN201280070682.2A patent/CN104145349A/en active Pending
- 2012-12-27 JP JP2014549527A patent/JP2015510220A/en active Pending
- 2012-12-27 TW TW101150511A patent/TW201345015A/en unknown
- 2012-12-27 KR KR20147020702A patent/KR20140116148A/en not_active Application Discontinuation
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See references of WO2013098532A1 * |
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US20140332795A1 (en) | 2014-11-13 |
WO2013098532A1 (en) | 2013-07-04 |
KR20140116148A (en) | 2014-10-01 |
FR2985092A1 (en) | 2013-06-28 |
JP2015510220A (en) | 2015-04-02 |
CN104145349A (en) | 2014-11-12 |
FR2985091B1 (en) | 2014-01-10 |
FR2985092B1 (en) | 2014-01-10 |
TW201345015A (en) | 2013-11-01 |
FR2985091A1 (en) | 2013-06-28 |
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