EP2783402A1 - Substrate with a functional layer comprising a sulphurous compound - Google Patents
Substrate with a functional layer comprising a sulphurous compoundInfo
- Publication number
- EP2783402A1 EP2783402A1 EP12774994.3A EP12774994A EP2783402A1 EP 2783402 A1 EP2783402 A1 EP 2783402A1 EP 12774994 A EP12774994 A EP 12774994A EP 2783402 A1 EP2783402 A1 EP 2783402A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- functional layer
- substrate
- silver
- support
- 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- Withdrawn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
- 239000002346 layers by function Substances 0.000 title claims abstract description 75
- 239000000758 substrate Substances 0.000 title claims abstract description 50
- 150000001875 compounds Chemical class 0.000 title abstract description 23
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 165
- 229910052751 metal Inorganic materials 0.000 claims description 56
- 239000002184 metal Substances 0.000 claims description 56
- 238000002161 passivation Methods 0.000 claims description 44
- 229910052709 silver Inorganic materials 0.000 claims description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 38
- 239000004332 silver Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 17
- 230000003287 optical effect Effects 0.000 claims description 14
- 230000004888 barrier function Effects 0.000 claims description 13
- 238000005457 optimization Methods 0.000 claims description 12
- 230000005693 optoelectronics Effects 0.000 claims description 12
- -1 thiosulphate anions Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000010329 laser etching Methods 0.000 claims description 10
- 238000003780 insertion Methods 0.000 claims description 8
- 230000037431 insertion Effects 0.000 claims description 8
- 150000003464 sulfur compounds Chemical class 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 abstract 1
- 229910021653 sulphate ion Inorganic materials 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 43
- 239000010936 titanium Substances 0.000 description 34
- 229910052725 zinc Inorganic materials 0.000 description 28
- 150000004767 nitrides Chemical class 0.000 description 25
- 229910052782 aluminium Inorganic materials 0.000 description 23
- 229910052719 titanium Inorganic materials 0.000 description 23
- 229910052726 zirconium Inorganic materials 0.000 description 19
- 229910052804 chromium Inorganic materials 0.000 description 18
- 150000001247 metal acetylides Chemical class 0.000 description 18
- 239000011521 glass Substances 0.000 description 15
- 229910052718 tin Inorganic materials 0.000 description 15
- 229910052735 hafnium Inorganic materials 0.000 description 14
- 229910052750 molybdenum Inorganic materials 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 229910052758 niobium Inorganic materials 0.000 description 13
- 239000010955 niobium Substances 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 229910052720 vanadium Inorganic materials 0.000 description 12
- 238000007654 immersion Methods 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 11
- 229910052738 indium Inorganic materials 0.000 description 9
- 229910052715 tantalum Inorganic materials 0.000 description 9
- 229910052787 antimony Inorganic materials 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000003989 dielectric material Substances 0.000 description 8
- 239000002019 doping agent Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 238000001124 conductive atomic force microscopy Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 238000010147 laser engraving Methods 0.000 description 6
- 238000000386 microscopy Methods 0.000 description 6
- 230000000877 morphologic effect Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229940048910 thiosulfate Drugs 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical class O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 229910001120 nichrome Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000010944 silver (metal) Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 229910018487 Ni—Cr Inorganic materials 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000013086 organic photovoltaic Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 239000003586 protic polar solvent Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000012487 rinsing solution Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910008651 TiZr Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 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 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ZARVOZCHNMQIBL-UHFFFAOYSA-N oxygen(2-) titanium(4+) zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4] ZARVOZCHNMQIBL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 210000004694 pigment cell Anatomy 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide 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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/621—Providing a shape to conductive layers, e.g. patterning or selective deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
- H01L21/461—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/4763—Deposition of non-insulating, e.g. conductive -, resistive -, layers on insulating layers; After-treatment of these layers
- H01L21/47635—After-treatment of these layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- 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
-
- 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
- H10K50/84—Passivation; Containers; Encapsulations
-
- 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
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- Functional layer substrate comprising a sulfur compound
- the field of the invention is that of substrates comprising a functional layer conferring electrical conduction properties.
- the invention relates to a substrate comprising an electrical conduction functional layer, said functional layer comprising a sulfur-containing interfacial compound.
- the present invention also relates to the processes for manufacturing these substrates as well as to the optoelectronic devices in which these substrates are incorporated.
- organic electroluminescent devices known by the acronym OLED (organic light emitting device), light collecting devices such as organic photovoltaic cells known by the acronym OPV (Organic Photovoltaic) organic thin film transistors known by the acronym OTFT (organic thin-film transistor) or solar cells Grâzel also called photosensitive pigment cells known by the acronym DSSC (Dye Sensitized Solar Cells), preferably, is meant to designate organic electroluminescent devices.
- OLED organic light emitting device
- OPV Organic Photovoltaic cells
- OTFT organic thin-film transistor
- DSSC Dynamic Sensitized Solar Cells
- Substrates comprising a functional layer conferring electrical conduction properties are obtained in particular by magnetron sputtering deposition of said functional layer on a support.
- the use of this type of technique makes it possible to obtain surfaces of low roughness.
- the substrates comprising a functional layer conferring electrical conduction properties used in various optoelectronic devices have a discontinuity in the form of an etching.
- the conductive layer etching is a critical element for the proper functioning of devices made from such structures. This etching makes it possible to delimit the optoelectronic modules and its quality is essential to ensure the preservation of their optical and / or electrical properties.
- the etching can be performed using a laser beam.
- the laser beam is responsible for significant electrical leakage. These leakage currents have the effect of limiting the efficiency performance and the lifetime of the optoelectronic devices.
- OLED Organic Light Emitting Device
- shiny edge phenomena are thus observed under application of a voltage. These phenomena are due to major changes in the nature of the materials used in the conductive functional layer and the topographic modification, in other words thickness, of this by the laser beam. More particularly when said layer is based on a stack comprising one or more dielectric layer / metal layer / dielectric layer successions.
- wet etching solutions are already known for improving the topographic laser etching properties of certain conductive layers, more particularly transparent conductive layers, used in various optoelectronic applications.
- acid-based solutions such as HCl, HBr, etc.
- FeCl 3 and H 2 O are used for the "wet etching" of the functional layer comprising a silver layer.
- Such examples of solutions are described in the articles by Y. Aoshima et al., "Development of silver-based multilayer coating electrodes with low resistance for use in fiât panel displays ", Jpn. J. Appl. Phys., Vol. 39, pp. 4884-4889 (2000) and Y.
- the invention in at least one of its embodiments, also aims to provide a substrate comprising a functional layer comprising at least one metal layer and conferring electrical conduction properties, said layer being discontinuous, the discontinuity being more particularly obtained by a laser engraving.
- the invention also aims to implement a functional layer passivation treatment method comprising at least one metal layer, said functional layer being etched mechanically (for example by scratching) or laser but also to implement a post-treatment after laser etching allowing to reduce not only the graphical topographic damage induced by the action of the laser beam but also leading to the isolation of laser etching edges of the functional layer comprising at least one metal layer.
- the present invention also aims to provide an optoelectronic device incorporating a substrate in accordance with the the present invention, more particularly an organic light-emitting diode or an organic photovoltaic cell.
- the invention relates to a substrate comprising a support, said support comprising on at least one of its main faces, a functional layer conferring electrical conduction properties, said functional layer comprising at least one metal layer.
- such a functional layer has at its extreme surface opposite the support (that is to say the outermost surface of the functional layer relative to the support or the surface of the functional layer furthest from the support), at least one sulfur compound in the form of thio sulfate.
- the general principle of the invention is based on the presence at the extreme surface of the functional layer of at least one sulfur compound in the form of thiosulphate, the presence of said sulfur compound permitting passivation of the surface of the functional layer.
- the invention is based on a completely new and inventive approach to passivation of the functional layer, the inventors having determined that surprisingly the presence of a sulfur compound at the extreme surface allows such passivation.
- Presence of an sulfur compound at the extreme surface is meant a sulfur content expressed as an atomic percentage of at least 0.4% over a thickness of 10 nm, said percentage being measured by spectroscopy of XPS electron photo.
- the support on which the functional layer is deposited is preferably rigid.
- the function of the support is to support and / or protect the functional layer.
- the support comprises at least a total or partial structuring surface on at least one of its faces.
- the structuring of the support comprises at least one of the processes selected from etching, rolling and / or laser etching.
- the chemical etching of the support comprises at least the matting and / or etching (for example by etching with hydrofluoric acid of a silicosodocalcic glass).
- the rolling method comprises at least the step of structuring the substrate by the pressure impression of a pattern using at least one printing roll.
- the substrate may be glass, rigid plastics material (eg organic glass, polycarbonate) or flexible polymeric films (eg polyvinyl butyral (PVB), polyethylene terephthalate (PET), vinyl acetate copolymer and ethylene (EVA)).
- the support is a glass sheet.
- the glasses are mineral or organic.
- the mineral glasses are preferred.
- the clear or colored silicosodocalcic glasses are preferred in the mass or on the surface. More preferably, they are extra clear silicosodocalcic glasses.
- extra clear means a glass containing at most 0.020% by weight of the total Fe glass expressed in Fe 2 0 3 and preferably at most 0.015% by weight.
- the support preferably has a geometric thickness of at least 0.35 mm. By the terms “geometrical thickness”, one understands the average physical thickness.
- layer in the sense of the present invention, it is meant that said layer may consist of a layer of single material or a plurality of layers each of a different material.
- the functional layer may thus be an electrical conduction layer comprising at least one metal layer based on silver, the silver being present in pure form or alloyed with another metal, the pure form being preferred.
- the electrical conduction functional layer comprises at least one silver-based metal layer
- said silver-based metal layer is protected on both sides by at least one oxide or nitride-based layer.
- the other metal preferably comprises at least palladium and / or gold, more preferably palladium.
- the layer functional is a functional layer of electrical conduction comprising at least one metal layer based on silver, said layer also comprises a set of dielectric layers disposed on either side of said silver-based metal layer.
- the silver-based metal layer has a geometric thickness of at least 5.0 nm, preferably at least 9.0 nm.
- the silver-based metal layer has a geometric thickness of at most 25.0 nm, preferably at most 18.0 nm, more preferably at most 14.0 nm.
- the metal layer based on silver has a thickness equal to 12.5 nm.
- the electrical conductivity layer may comprise several silver-based metal layers, preferably two silver-based metal layers, said layers being separated by dielectric layers making the support covered with a functional layer according to the invention. Reflective in a part of the spectrum of solar radiation, in particular in the field of visible lengths.
- sunscreen functional layer the products marketed under the name of "Stopray” by the company AGC and as an example of low-emitting coating products marketed under the term "TopN, TopN +, TopN + T" by the same company.
- the functional electric conduction layer, low emissive or antisolar comprising at least one silver-based metal layer also comprises at least one means of chemical protection of said silver layer.
- chemical protection is intended to denote protection against any phenomenon of chemical degradation of silver (oxidation, diffusion of alkaline ions from the glass sheet, diffusion of silver during quenching heat treatment) .
- these means for example:
- At least one barrier layer said barrier layer being, with respect to the glass sheet, the first layer constituting the functional layer of electrical conduction, low emissive or antisolar.
- the material constituting the barrier layer being selected from titanium oxide, zinc oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum nitride, aluminum oxynitride, aluminum oxide, this barrier layer being optionally doped or alloyed with tin.
- the barrier layer has a geometric thickness of at least 3.0 nm, preferably at least 10.0 nm, more preferably at least 30.0 nm, even more preferably at least 50.0 nm.
- the barrier layer has a thickness of at most 100 nm.
- At least one sacrificial layer the sacrificial layer being located on at least one face of the silver-based metal layer.
- sacrificial layer is meant a layer that can be oxidized in whole or in part. This layer makes it possible to avoid deterioration of the silver layer, in particular by oxidation.
- the sacrificial layer comprises at least one compound chosen from metals, nitrides, oxides and sub-stoichiometric oxygen oxides.
- the metals, nitrides, oxides and sub-stoichiometric metal oxides comprise at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al.
- the sacrificial layer comprises at least Ti, TiO x (with x ⁇ 2) or NiCr.
- the thickness of the sacrificial layer is at least 0.5 nm.
- the thickness of the sacrificial layer is at most 6.0 nm. More preferably, the thickness is between 1.0 and 2.5 nm.
- a sacrificial layer is deposited on the face of the silver metal layer furthest away from the support.
- the substrate according to the invention is such that the functional layer of electrical conduction comprises a thin layer of uniformity of the surface electrical properties, said uniformization layer being the furthest layer of the support within of the diaper functional.
- the main function of the uniformization layer is to obtain a uniform charge transfer over the entire surface of the functional layer. This uniform transfer results, when the conductive functional layer is used as an electrode in an OLED device, by an equivalent emitted or converted light flux at any point on the surface. It also increases the life of optoelectronic devices since this transfer is the same at each point, eliminating possible hot spots.
- the uniformization layer has a geometric thickness of at least 0.5 nm, preferably at least 1.0 nm.
- the uniformity layer has an angular frequency of at most 5.0 nm, preferably at most 2.5 nm, more preferably at most 2.0 nm. More preferably, the uniformization layer is equal to 1.5 nm.
- the uniformization layer comprises at least one layer comprising at least one inorganic material selected from a metal, a nitride, an oxide, a carbide, an oxynitride, an oxycarbide, a carbonitride, an oxycarbonitride and the mixtures of at least two of them.
- the inorganic material of the uniformization layer comprises a single metal or a mixture of metals.
- the generic term "metal mixture” refers to combinations of two or more metals in the form of an alloy or a doping of at least one metal with at least one other metal.
- the uniformization layer comprises at least those belonging to columns 1, 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 of the table of the periodic table of elements in its version published by IUPAC, June 22, 2007.
- the metal and / or metal mixture comprises at least one element selected from Li, Na, K, Rb, Mg, Ca, Sr, Ba, Ti, Zr, Hf, V, Nb.
- the metal or the mixture of metals comprises at least one element selected from C, Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, Zn.
- the metal mixture preferably comprises Ni-Cr and / or Zn doped with Al.
- the inorganic material of the uniformization layer is present in the form of at least one chemical compound selected from carbides, carbonitrides, oxynitrides, oxycarbides, oxycarbonitrides and mixtures of at least two of them.
- the oxynitrides, oxycarbides and oxycarbonitrides of the uniformization layer may be in non-stoichiometric form, preferably substoichiometric with respect to oxygen.
- Carbides, carbonitrides, oxynitrides, oxycarbides and oxycarbonitrides are carbides, carbonitrides, oxynitrides, oxycarbides and oxycarbonitrides of at least one element selected from those belonging to columns 2, 4, 6, 7, 8, 9, 10, 11, 12, 13, 14 of the table of the periodic table of the elements in its version published by IUPAC, on June 22, 2007.
- these are carbides, carbonitrides, oxynitrides, oxycarbures, oxycarbonitrides of at least one element selected from Ti , Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si.
- the uniformizing thin film comprises at least one oxynitride comprising at least one element selected from Ti, Zr, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au. , Zn, C d, Al, S i.
- the thin film of uniformity of the electrical properties of surface comprises at least one oxynitride selected from Ti oxynitride, Zr oxynitride, Ni oxynitride, NiCr oxynitride.
- the inorganic material of the uniformization layer is present in the form of at least one metal nitride of at least one element selected from those belonging to columns 4, 5, 6, 7, 8 , 9, 10, 1 1, 12, 13, 14 of the table of the periodic table of elements in its version published by IUPAC, on June 22, 2007.
- the standardization layer comprises at least one nitride of a element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si.
- the nitride comprises at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, Zn. More preferably, the thin film of uniformity of the surface electrical properties comprises at least Ti nitride, Zr nitride, Ni nitride, NiCr nitride.
- the inorganic material of the uniformization layer is present in the form of at least one metal oxide of at least one element selected from those belonging to columns 4, 5, 6, 7, 8 , 9, 10, 1 1, 12, 13, 14 of the table of the periodic table of elements in its version published by IUPAC, on June 22, 2007.
- the uniformization layer comprises at least one oxide of a element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, In, Si, Sn. More preferably, the oxide comprises at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, In, Sn, Zn.
- the oxide of the uniformization layer may be an oxide under stoichiometric oxygen.
- the oxide optionally comprises at least one doping element.
- the doping element is selected from at least one of the elements selected from Al, Ga, In, Sn, Sb, and F.
- the thin film of uniformity of the electrical properties of surface comprises at least the Ti oxide and / or the Zr oxide and / or the Ni oxide and / or the NiCr oxide and / or ⁇ and / or the doped Sn oxide, the dopant being at least one element selected from F and Sb, and / or doped Zn oxide, the dopant being at least one element selected from Al, Ga, Sn, Ti.
- the substrate according to the invention is such that the electrical conduction functional layer comprises a layer inserted between the silver-based metal layer and the uniformization layer comprising at least one inorganic chemical compound.
- This insertion layer has the function of forming part of an optical cavity making it possible to make the metal layer based on transparent silver.
- the term inorganic chemical compound comprises at least one dielectric compound and / or at least one electrically conductive compound.
- the dielectric compound comprises at least one compound chosen from oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides and mixtures of at least two of them.
- the oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides or oxycarbonitrides of the dielectric compound are oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides or oxycarbonitrides of at least one element selected from Ti, Zr, Hf, Ta, Cr, Mo, Zn, Ai, In, Si, Sn, Sb, Bi.
- the dielectric compound preferably comprises a titanium oxide, a zinc oxide, a tin oxide, an aluminum nitride, a silicon nitride and / or a silicon carbide.
- the conductor comprises at least one compound chosen from oxides in stoichiometric oxygen, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides, doped oxycarbonitrides and than the mixtures of at least two of them.
- the stoichiometric oxides, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides or doped oxycarbonitrides of the conducting compound are sub stoichiometric oxides, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides or doped oxycarbonitrides of at least one element selected from Ti, Zr, Ta, Cr, Mo, Zn, Al, In, Si, Sn , the Sb.
- the dopants comprise at least one of the elements chosen from Al, Ga, In, Sn, P, Sb and F. More preferably, the conducting compound comprises at least ⁇ and / or oxide. doped Sn, the dopant being at least one element selected from F and Sb, and / or doped Zn oxide, the dopant being at least one element selected from A 1, Ga, Sn, Ti .
- the inorganic chemical compound comprises at least ZnO x (with x ⁇ 1) and / or Zn x Sn y O z (with x + y> 3 and z ⁇ 6).
- the Zn x Sn y O z comprises at most 95% by weight of zinc, the weight percentage of zinc is expressed relative to the total weight of the metals present in the layer.
- the insertion layer has a geometric thickness of at least 3.0 nm.
- the insertion layer has a geometric thickness of at most 50.0 nm, preferably at most 20.0 nm, more preferably at most 10.0 nm.
- the substrate according to the invention is such that the electrical conduction functional layer comprises at least one optical optimization layer inserted between the silver-based metal layer and the support.
- This optimization layer makes it possible, thanks to its thickness and its chemical nature, to obtain a high light flux.
- It comprises at least one inorganic chemical compound.
- the term inorganic chemical compound comprises at least one dielectric compound and / or at least one electrically conductive compound.
- the dielectric compound comprises at least one compound chosen from oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides and mixtures of at least two of them.
- the oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides or oxycarbonitrides of the dielectric compound are oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides or oxycarbonitrides of at least one element selected from Ti, Zr, Hf, Nb, Ta, Cr, Mo, Zn, Ai, In, Si, Sn, Sb, Bi.
- the dielectric compound preferably comprises a titanium oxide, a zirconium oxide, a hafnium oxide, a niobium oxide, a tantalum oxide, a zinc oxide, an aluminum nitride, a silicon nitride and / or silicon carbide.
- the conductor comprises at least one compound chosen from oxides in stoichiometric oxygen, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides, doped oxycarbonitrides and than the mixtures of at least two of them.
- the stoichiometric oxides, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides or doped oxycarbonitrides of the conducting compound are sub stoichiometric oxides, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides or doped oxycarbonitrides of at least one element selected from Ti, Zr, Ta, Cr, Mo, Zn, Al, In, Si, Sn , the P, the Sb.
- the dopants comprise at least one of the elements chosen from Al, Ga, In, Sn, Sb and F. More preferentially, the conducting compound comprises at least TITO and / or doped Sn oxide. , the dopant being at least one element selected from F and Sb, and / or doped Zn oxide, the dopant being at least one element selected from Al, Ga, Sn, Ti.
- the inorganic chemical compound comprises at least ZnO x (with x ⁇ 1) and / or Zn x Sn y O z (with x + y> 3 and z ⁇ 6).
- the Zn x Sn y O z comprises at most 95% by weight of zinc, the weight percentage of zinc is expressed relative to the total weight of the metals present in the layer.
- the optical optimization layer has a geometric thickness of at least 3.0 nm, preferably at least 10.0 nm, more preferably at least 30.0 nm, even more preferably at least 50, 0 nm.
- the optical optimization layer has a thickness of at most 100 nm.
- the substrate according to the invention is such that the electrical conduction functional layer comprises at least one additional crystallization layer inserted between the support and the silver-based metal layer. This layer allows a preferential growth of the silver-based metal layer and thus makes it possible to obtain good electrical and optical properties of said layer.
- the term inorganic chemical compound comprises at least at least ZnO x (with x ⁇ 1) and / or Zn x Sn y O z (with x + y> 3 and z ⁇ 6).
- the Zn x Sn y O z comprises at most 95% by weight of zinc, the weight percentage of zinc is expressed relative to the total weight of the metals present in the layer.
- the crystallization layer has a geometric thickness of at least 3.0 nm.
- the crystallization layer has a thickness of at most 50.0 nm, preferably at most 20.0 nm, more preferably at most 10.0 nm.
- the crystallization layer is merged with the barrier layer and / or the optical optimization layer.
- the sum of the geometric thicknesses of the barrier, optical optimization and crystallization layers is at least 3.0 nm, preferably at least 10.0 nm, more preferably from minus 30.0 nm, still more preferably at least 50.0 nm.
- the sum of the thicknesses of the layers has at most 100 nm.
- barrier and crystallization layers at least one of these two layers is merged with the optical optimization layer.
- the barrier, optimization, crystallization and insertion layers may be of the same chemical nature or of a different chemical nature.
- the terms "different chemical nature” do not exclude the possibility of combinations of type: 3 layers of identical nature and one of a different nature or two layers of identical nature, the two remaining layers being indifferently identical in nature to each other or to different nature.
- the substrate according to the invention is such that it comprises between the support and the uniformization layer, at least one additional stack: silver-based metal layer, insertion layer.
- This stack can be reproduced n times, with n representing an integer greater than or equal to 1.
- the stack constituting the functional electrical conduction layer is preferably a stack comprising from one to three silver-based metal layers, preferably one or two silver-based metal layers.
- the substrate according to the invention essentially has the following structure from the support:
- Barrier layer and optical optimization layer combined: thickness 50-80 nm in Ti0 2 ;
- Crystallization layer thickness 3-20 nm in Zn x Sn y O z as previously defined
- Silver-based metal layer 8-14nm thick in pure Ag
- Insertion layer thickness 3-20nm in Zn x Sn y O z as previously defined
- Standardization layer thickness 0.5-3 nm in X with X: Li, Mg, Cu, Ti, Zr, Hf, V, Nb, Ta, Ni, Pd, Cr, Mo, Al, Zn, Ni-Cr or Zn doped with Al, in nitride of X with X: Ti, Zr, Hf, V, Nb, Ta, Ni, Pd, Cr, Mo, Al, Zn, Ni-Cr, in oxynitride of X with X: Ti , Zr, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si or NiCr, to X oxide with X: Ti, Zr, Hf, V , Nb, Ta, Ni, Pd, Cr, Mo, Al, Zn, Ni-Cr or Zn doped with Al.
- the substrate according to the invention is such that the functional layer is a discontinuous layer in the form of distinct adjacent zones, in particular in the form of parallel strips.
- the substrate according to the invention is such that said discontinuous functional layer exhibits a thickness variation of the zone medium at the zone edges of less than 30%, preferably less than 15%, most preferably less than 5%, most preferably less than 1%.
- the substrate according to the invention is an anode for optoelectronic devices, more preferably for an organic electroluminescent device (OLED).
- OLED organic electroluminescent device
- the invention relates to a method of passivating the surface of a substrate provided with a functional layer such that it comprises the following successive stages:
- Step of depositing the functional layer on at least a part of the support
- a rinsing step with a protic polar solvent, preferably a water-based solvent.
- the deposition step of the functional layer is carried out by cathodic sputtering, possibly assisted by a magnetic field.
- the deposition process is carried out under vacuum.
- under vacuum denote a pressure less than or equal to 1, 2 P a.
- the vacuum process is a magnetic field assisted sputtering technique.
- the passivation solution comprising thiosulfate anions used during the passivation step is preferably a solution based on a protic polar solvent, the preferred solvent being water, more preferably deionized water. Water makes it possible to obtain higher thiosulphate concentrations on the one hand and to avoid carbon contamination of the surface on the other hand.
- the passivation solution is a solution comprising a concentration of thiosulphate anion at least greater than or equal to 0.1 M, preferably at least greater than or equal to 0.5 M, more preferably at least greater than or equal to 0.8 M, most preferably of the order of 1.0 M.
- the passivation solution is based on thiosulfate anions.
- the term "based on” is intended to mean that the thiosulphate anions represent at least 50% of the concentration of the anions present in the passivation solution.
- the thiosulphate salts used for the preparation of the passivation solution are K and / or Na thiosulphates.
- the passivation solution is a solution containing only thiosulphate anions, the other anions likely to be present being only in trace form.
- the passivation solution is a 1.0 M aqueous solution of Na thiosulfate.
- the application of the passivation solution can be carried out by application techniques in roll, spray, curtain or immersion. In the case of an immersion application, it is meant an immersion of the substrate covered with the stack of layers in the passivation solution.
- the passivation solution may be stirred during immersion, the stirring being mechanical or ultrasonic agitation, preferably the stirring is ultrasonic for reasons of uniformization of the solvent flow to the surface of the functional layer to be passivated.
- the solution is not agitated, the absence of agitation allowing better control of the passivation.
- the protic polar solvent used during the optional rinsing step is preferably water, more preferably deionized water, deionized water, it is meant water having a conductivity at most less than or equal to 1 ⁇ 8 / ⁇ . Water makes it possible to obtain higher concentrations of thiosulphate anions and to avoid carbon contamination of the surface.
- the application of the rinsing solution can be carried out by the application techniques in roll, spray, curtain or immersion. In the case of an immersion application, it is intended to immerse the substrate in the rinsing solution.
- the rinsing solution is stirred during the immersion, the stirring being mechanical or ultrasonic agitation.
- the stirring is ultrasonic, the inventors having determined that, surprisingly, the ultrasonic rinsing also contributes to a uniformization of the surface of the functional layer.
- the passivation method of the surface of a substrate provided with a functional layer according to the invention is such that it comprises between the deposition steps of the functional layer and the step passivation, an additional step of etching, said etching being mechanical or laser.
- the etching is a laser engraving.
- the etching step allows obtaining a discontinuous functional layer.
- this step induces the appearance of peaks at the surface of the functional layer, more particularly at the edges of the etching zones, said peaks possibly causing an increase of up to 200% in the initial thickness of the functional layer.
- the inventors have determined that, surprisingly, the step of passivation of the surface by application of a passivation solution comprising thiosulphate anions, advantageously followed by a rinsing step with a protic polar solvent, leads to a reduction or even a disappearance of said peaks.
- a third subject of the invention relates to an optoelectronic device comprising a substrate according to the invention.
- Figure 1 shows a morphological observation of a laser engraving line by 3D microscopy
- FIG. 2 illustrates the effect of morphology resulting from laser etching on a low ignition voltage OLED device by the presence of shiny edges (A) and presents a simplified diagram of the device studied (B),
- FIG. 3 shows the effect of passivation on the morphology of the etched layer, before (3A, 3B) and after passivation (3C, 3D)
- FIG. 4 is a C-AFM measurement illustrating the effect of the passivation on the conductivity of the etching edges
- FIG. 5 is a topographic observation by 3D microscopy of a laser etching line before passivation, after 5 minutes of immersion in the passivation solution and after 15 minutes of passivation,
- Figure 6 is a topographic observation by 3D microscopy after passivation of 5 min, with (B) / without use (A) of ultrasound during rinsing
- FIG. 7 schematically represents an example of a substrate according to the invention
- a functional electrical conduction layer having as structure from the support:
- Ti0 2 (65.0 nm) / Zn x Sn y O z (5.0 nm) / Ag (12.5 nm) / Ti (2.5 nm) / Zn x Sn y O z (7.0 nm)
- Ti / Nitride (1.5 nm) was sputtered onto a clear glass support having a thickness of 1.60 mm.
- the deposit conditions for each of the layers are as follows:
- TiO 2 -based layers are deposited using a titanium target at a pressure of 0.5 Pa in an Ar / O 2 atmosphere.
- the layers based on Zn x Sn y O z are deposited using a ZnSn alloy target, at a pressure of 0.5 Pa in an Ar / O 2 atmosphere, the Ag layers are deposited using an Ag target, at a pressure of 0.5 Pa in an Ar atmosphere, the Ti-based layers are deposited using a Ti target, under a pressure of 0.5 Pa in an Ar atmosphere and can be partially oxidized by the following Ar / O 2 plasma, The uniformity layer of Ti nitride-based electrical surface properties is deposited using a Ti target at a pressure of 0.5 Pa in an Ar / N 2 80/20 atmosphere.
- Said layer then underwent laser engraving using a laser of the Edgewave brand.
- the characteristics of the laser used for etching are shown in Table I.
- Figure 1 shows the effect of the laser beam on the functional layer.
- the functional layer undergoes characteristic topographic damage resulting in particular by the formation of morphological peaks corresponding to an increase up to 200% of the initial thickness of the layer.
- the leakage currents correspond to currents flowing in the opposite direction of the current enabling operation of the OLED device. They are calculated on the basis of current densities (mA / cm 2 ) measured at -5V.
- the substrate obtained is then immersed in a 1M aqueous solution of Na thiosulphate in the absence of stirring for 10 minutes at room temperature.
- the topographic repair and electrical passivation effects obtained are as shown in FIGS. 3 and 4.
- a clear reduction or even the complete disappearance of the morphological peaks formed under the action of the laser beam (FIG. 3) is associated with the electrical isolation of the laser etching edges observed in c-AFM (Fig. 4).
- C-AFM Conductive Atomic Force Microscopy
- the microscope is used in confocal mode, that is, the 3D representation of the observed sample is reconstructed from a set of images made at different depths in the sample. These sections are obtained by positioning the focal plane of the lens at these different depths.
- C-AFM measurements were performed on a Veeco branded device.
- Conductive AFM makes it possible to simultaneously capture the topographic image and the electrical image (conductivity measurement) of the observed sample.
- the characteristics of the apparatus used are shown in Table II.
- the chemical composition of the passivation solution, its concentration of thiosulfate and its temperature are adjusted so as to remove only the pile of surface materials present at the laser etching edges, without affecting the active surface of the functional layer of electrical conduction.
- Figure 5 illustrates the topographic observation of a laser engraving line by 3D microscopy before immersion in the passivation solution after 5 minutes and after 15 minutes of immersion. The appearance of secondary peaks after 15 minutes of immersion is noted.
- Table IV briefly shows the effect of the concentration of the passivation solution as a function of the treatment time, said treatment being carried out at room temperature ( ⁇ 25 ° C.):
- FIG. 6 represents an example of a substrate (1), said substrate comprising a support 10 and a functional layer (1 1), said functional layer comprising successively from the support (10):
- substrates comprising a glass support and a low emissivity type functional layer that can be subjected to said passivation treatment are shown in Table IV.
- Table IV Examples of substrates that can be passivated, said substrate consisting of an extra-clear glass support covered by one of the following functional layers: TABLE IV
- ZS05 zinc tin mixed oxide obtained by cathodic sputtering in an oxidizing atmosphere from a metal target of a ZnSn alloy at 52% Zn and 48% Sn
- ZS09 zinc tin mixed oxide obtained by sputtering in an oxidizing atmosphere from a metal target of a ZnSn alloy at 90% Zn and 10% Sn
- TZO mixed titanium zirconium oxide obtained by cathodic sputtering in an oxidizing atmosphere from a metal target of a TiZr alloy at 50% Ti and 50% Zr
Abstract
The invention relates to a substrate (1) comprising a medium (10), said medium (10) comprising, on at least one of its main faces, a functional layer (11) that has low-E or antisolar properties or is electrically conductive, characterized in that said functional layer (11) comprises, on its extreme surface opposite the medium (10), at least one sulphurous compound, in particular a sulphate, a sulphonate and/or a thiosulphate.
Description
Substrat à couche fonctionnelle comprenant un composé soufré Functional layer substrate comprising a sulfur compound
1. Domaine de l'invention 1. Field of the invention
Le domaine de l'invention est celui des substrats comprenant une couche fonctionnelle conférant des propriétés de conduction électrique. The field of the invention is that of substrates comprising a functional layer conferring electrical conduction properties.
Plus précisément, l'invention concerne un substrat comprenant une couche fonctionnelle de conduction électrique, ladite couche fonctionnelle comprenant un composé interfacial soufré. La présente invention se rapporte également aux procédés de fabrication de ces substrats ainsi qu'aux dispositifs optoélectroniques dans lesquels ces substrats sont incorporés More specifically, the invention relates to a substrate comprising an electrical conduction functional layer, said functional layer comprising a sulfur-containing interfacial compound. The present invention also relates to the processes for manufacturing these substrates as well as to the optoelectronic devices in which these substrates are incorporated.
Par les termes « dispositifs optoélectroniques », on entend désigner des dispositifs organiques électroluminescents connus sous l'acronyme OLED (organic light emitting device), des dispositifs collecteurs de lumière tels que les cellules photo voltaïques organiques connues sous l'acronyme OPV (Organic Photovoltaïcs), des transistors organiques en couches minces connus sous l'acronyme OTFT (organic thin-film transistor) ou bien des cellules solaires Grâzel appelée également cellules à pigment photosensible connues sous l'acronyme DSSC (Dye Sensitized Solar Cells), préférentiellement, on entend désigner des dispositifs organiques électroluminescents. By the term "optoelectronic devices" is meant organic electroluminescent devices known by the acronym OLED (organic light emitting device), light collecting devices such as organic photovoltaic cells known by the acronym OPV (Organic Photovoltaic) organic thin film transistors known by the acronym OTFT (organic thin-film transistor) or solar cells Grâzel also called photosensitive pigment cells known by the acronym DSSC (Dye Sensitized Solar Cells), preferably, is meant to designate organic electroluminescent devices.
2. Solutions de l'art antérieur 2. Solutions of the prior art
Les substrats comprenant une couche fonctionnelle conférant des propriétés de conduction électrique sont notamment obtenus par dépôt par pulvérisation cathodique magnétron de ladite couche fonctionnelle sur un support. L'utilisation de ce type de technique permet d'obtenir des surfaces de faible rugosité. Toutefois, les substrats comprenant une couche fonctionnelle conférant des propriétés de conduction électrique utilisés dans divers dispositifs optoélectroniques présentent une discontinuité sous la forme d'une gravure. La
gravure de couches conductrices est un élément critique pour le bon fonctionnement des dispositifs élaborés à partir de telles structures. Cette gravure permet de délimiter les modules optoélectroniques et sa qualité est primordiale pour assurer la préservation de leurs propriétés optiques et/ou électriques. La gravure peut être réalisée à l'aide d'un faisceau laser. Substrates comprising a functional layer conferring electrical conduction properties are obtained in particular by magnetron sputtering deposition of said functional layer on a support. The use of this type of technique makes it possible to obtain surfaces of low roughness. However, the substrates comprising a functional layer conferring electrical conduction properties used in various optoelectronic devices have a discontinuity in the form of an etching. The conductive layer etching is a critical element for the proper functioning of devices made from such structures. This etching makes it possible to delimit the optoelectronic modules and its quality is essential to ensure the preservation of their optical and / or electrical properties. The etching can be performed using a laser beam.
Dans les conditions standards d'utilisation, le faisceau laser est responsable de fuites de courant électrique importantes. Ces courants de fuites ont pour conséquence de limiter la performance en efficacité et la durée de vie des dispositifs optoélectroniques. Dans le cas des diodes électroluminescentes organiques connues sous l'acronyme OLED (Organic Light Emitting Device) des phénomènes de bords brillants sont ainsi observés sous application d'une tension. Ces phénomènes sont dus aux modifications importantes de la nature des matériaux utilisés dans la couche fonctionnelle de conduction et de l a modification topographique, en d'autres termes d'épaisseur, de celle-ci par le faisceau laser. Plus particulièrement lorsque ladite couche est à base d'un empilement comprenant une ou plusieurs successions de couche diélectrique/couche métallique/couche diélectrique. Il existe des moyens pour limiter ces problématiques comme l'utilisation de laser présentant des caractéristiques très particulières (p. ex. : irradiation pico-/femtoseconde ou utilisation de longueurs d'onde particulières comme dans l'UV). Néanmoins, ces techniques bien que de plus en plus disponibles sont dans certains cas non industrialisables. Under standard conditions of use, the laser beam is responsible for significant electrical leakage. These leakage currents have the effect of limiting the efficiency performance and the lifetime of the optoelectronic devices. In the case of organic light-emitting diodes known by the acronym OLED (Organic Light Emitting Device) shiny edge phenomena are thus observed under application of a voltage. These phenomena are due to major changes in the nature of the materials used in the conductive functional layer and the topographic modification, in other words thickness, of this by the laser beam. More particularly when said layer is based on a stack comprising one or more dielectric layer / metal layer / dielectric layer successions. There are ways to limit these issues, such as the use of lasers with very specific characteristics (eg: pico- / femtosecond irradiation or use of particular wavelengths as in UV). Nevertheless, these techniques, although increasingly available, are in some cases non-industrializable.
Différentes solutions dites solutions de « wet etching » sont déjà connues pour l'amélioration des propriétés topographiques de gravure laser de certaines couches conductrices, plus particulièrement de couches conductrices transparentes, utilisées dans diverses applications optoélectroniques. Ainsi des solutions à base d'acide (tels que HC1, HBr...), de FeCl3 et d'H20 sont utilisées pour le « wet etching » de couche fonctionnelle comprenant une couche en argent. De tels exemples de solutions sont décrits dans les articles de Y. Aoshima et Coll., « Development of silver-based multilayer coating électrodes with low résistance
for use in fiât panel displays », Jpn. J. Appl. Phys., Vol. 39, pp. 4884-4889 (2000) et de Y. Aoshima et Coll., « Improvement of alkali durability of silver-based multilayer coatings for use in fiât panel displays », Jpn. J. Appl. Phys., Vol. 40, pp. 4166-4170 (2001). Cependant ces solutions sont, de par leur nature, relativement agressives envers la couche fonctionnelle et peuvent conduire à la détérioration des matériaux, plus particulièrement à la surface de la couche fonctionnelle, lorsque celle-ci comporte un empilage de couches. Various solutions known as "wet etching" solutions are already known for improving the topographic laser etching properties of certain conductive layers, more particularly transparent conductive layers, used in various optoelectronic applications. Thus acid-based solutions (such as HCl, HBr, etc.), FeCl 3 and H 2 O are used for the "wet etching" of the functional layer comprising a silver layer. Such examples of solutions are described in the articles by Y. Aoshima et al., "Development of silver-based multilayer coating electrodes with low resistance for use in fiât panel displays ", Jpn. J. Appl. Phys., Vol. 39, pp. 4884-4889 (2000) and Y. Aoshima et al., "Improvement of alkali durability of silver-based multilayer coatings for use in panel display displays", Jpn. J. Appl. Phys., Vol. 40, pp. 4166-4170 (2001). However, these solutions are, by their nature, relatively aggressive towards the functional layer and can lead to the deterioration of materials, more particularly to the surface of the functional layer, when it comprises a stack of layers.
3. Objectifs de l'invention L'invention a notamment pour objectif de pallier ces inconvénients de l'art antérieur. 3. OBJECTIVES OF THE INVENTION The object of the invention is notably to overcome these disadvantages of the prior art.
Plus précisément, l'invention, dans au moins un de ses modes de réalisation, a encore comme objectif de fournir un substrat comprenant une couche fonctionnelle comprenant au moins une couche métallique et conférant des propriétés de conduction électrique, ladite couche étant discontinue, la discontinuité étant plus particulièrement obtenue par une gravure laser. More specifically, the invention, in at least one of its embodiments, also aims to provide a substrate comprising a functional layer comprising at least one metal layer and conferring electrical conduction properties, said layer being discontinuous, the discontinuity being more particularly obtained by a laser engraving.
L'invention a encore pour objectif de mettre en œuvre un procédé de traitement de passivation de couche fonctionnelle comprenant au moins une couche métallique, ladite couche fonctionnelle étant gravée mécaniquement (par exemple par griffure) ou par laser mais également de mettre en œuvre un posttraitement après gravure laser permettant permettant de réduire non seulement les dommages topo graphiques induits par l'action du faisceau laser mais conduisant également à l'isolation des bords de gravure laser de la couche fonctionnelle comprenant au moins une couche métallique. Finalement, la présente invention a encore comme objectif de fournir un dispositif optoélectronique incorporant un substrat conforme à la
présente invention, plus particulièrement une diode électroluminescente organique ou une cellule photovoltaïque organique. The invention also aims to implement a functional layer passivation treatment method comprising at least one metal layer, said functional layer being etched mechanically (for example by scratching) or laser but also to implement a post-treatment after laser etching allowing to reduce not only the graphical topographic damage induced by the action of the laser beam but also leading to the isolation of laser etching edges of the functional layer comprising at least one metal layer. Finally, the present invention also aims to provide an optoelectronic device incorporating a substrate in accordance with the the present invention, more particularly an organic light-emitting diode or an organic photovoltaic cell.
4. Exposé de l'invention 4. Presentation of the invention
Conformément à un mode de réalisation particulier, l'invention concerne un substrat comprenant un support, ledit support comprenant sur au moins une de ses faces principales, une couche fonctionnelle conférant des propriétés de conduction électrique, ladite couche fonctionnelle comprenant au moins une couche métallique. According to a particular embodiment, the invention relates to a substrate comprising a support, said support comprising on at least one of its main faces, a functional layer conferring electrical conduction properties, said functional layer comprising at least one metal layer.
Selon l'invention, une telle couche fonctionnelle comporte à son extrême surface opposée au support (c'est-à-dire la surface la plus externe de la couche fonctionnelle par rapport au support ou encore la surface de la couche fonctionnelle la plus éloignée du support), au moins un composé soufré sous la forme de thio sulfate. According to the invention, such a functional layer has at its extreme surface opposite the support (that is to say the outermost surface of the functional layer relative to the support or the surface of the functional layer furthest from the support), at least one sulfur compound in the form of thio sulfate.
Le principe général de l'invention repose sur la présence à l'extrême surface de la couche fonctionnelle d'au moins un composé soufré sous la forme de thiosulfate, la présence dudit composé soufré permettant une passivation de la surface de la couche fonctionnelle. The general principle of the invention is based on the presence at the extreme surface of the functional layer of at least one sulfur compound in the form of thiosulphate, the presence of said sulfur compound permitting passivation of the surface of the functional layer.
Ainsi, l'invention repose sur une approche tout à fait nouvelle et inventive de passivation de la couche fonctionnelle, les inventeurs ayant déterminé que de manière surprenant la présence d'un composé soufré à l'extrême surface permet une telle passivation. Par les termes «présence d'un composé soufré à l'extrême surface», on entend désigner un taux de soufre exprimé en pourcentage atomique d'au moins 0,4 % sur une épaisseur de 10 nm, ledit pourcentage étant mesuré par spectroscopie de photo électrons XPS. Le support sur lequel est déposé la couche fonctionnelle est préférentiellement rigide. La fonction du support est de supporter et/ou de protéger la couche fonctionnelle. Selon un mode particulier de réalisation, le
support comprend au moins une structuration totale ou partielle en surface sur au moins une de ses faces. Généralement, la structuration du support comprend au moins un des procédés sélectionnés parmi l'attaque chimique, le laminage et/ou la gravure laser. L'attaque chimique du support comprend au moins le matage et/ou la gravure (par exemple par attaque au moyen d'acide fluorhydrique d'un verre silicosodocalcique). Le procédé de laminage comprend au moins l'étape de structuration du substrat par l'empreinte sous pression d'un motif à l'aide d'au moins un rouleau imprimeur. Le substrat peut être en verre, en matière plastique rigide (par exemple : verre organique, polycarbonate) ou en films polymériques souples (par exemple : butyral de polyvinyle (PVB), polyéthylène téréphtalate (PET), copolymère d'acétate de vinyle et d'éthylène (EVA)). De préférence le support est une feuille de verre. Les verres sont minéraux ou organiques. Les verres minéraux sont préférés. Parmi ceux-ci , on préfère les verres silicosodocalciques clairs ou colorés dans la masse ou en surface. Plus préférentiellement, ce sont des verres silicosodocalciques extra clairs. Le terme extra clair désigne un verre contenant au plus 0,020% en poids du verre de Fe total exprimé en Fe203 et de préférence au plus 0,015% en poids. Le support a de préférence une épaisseur géométrique d'au moins 0,35 mm. Par les termes « épaisseur géométrique », on comprend l'épaisseur physique moyenne. Par le terme « couche » au sens de la présente invention, on entend désigner le fait que ladite couche peut être constituée d'une couche en matériau unique ou d'une pluralité de couches chacune en un matériau différent. La couche fonctionnelle peut ainsi être une couche de conduction électrique comprenant au moins une couche métallique à base d'argent, l'argent étant présent sous forme pure ou alliée à un autre métal, la forme pure étant préférée. Lorsque la couche fonctionnelle de conduction électrique comprend au moins une couche métallique à base d'argent, ladite couche métallique à base d'argent est protégée de part et d'autre, par au moins une couche à base d'oxyde ou de nitrure. Lorsque l'argent est présent sous forme alliée, l'autre métal comprend préférentiellement au moins le palladium et/ou l'or, plus préférentiellement le palladium. Lorsque la couche
fonctionnelle est une couche fonctionnelle de conduction électrique comprenant au moins une couche métallique à base d'argent, ladite couche comprend également un ensemble de couches diélectriques disposées de part et d'autre de ladite couche métallique à base d'argent. La couche métallique à base d'argent a une épaisseur géométrique d'au moins 5,0 nm, préférentiellement d'au moins 9,0 nm. La couche métallique à base d'argent a une épaisseur géométrique d'au plus 25,0 nm, préférentiellement d'au plus 18,0 nm, plus préférentiellement d'au plus 14,0 nm. Le plus préférentiellement, la couche métallique à base d'argent a une épaisseur égale à 12,5 nm. La couche e conductivité électrique, peut comprendre plusieurs couches métalliques à base d'argent, de préférence deux couches métalliques à base d'argent, lesdites couches étant séparées par des couches diélectriques rendant le support recouvert d'une couche fonctionnelle selon l'invention anti-réfléchissante dans une partie du spectre du rayonnement solaire, en particulier dans le domaine des longueurs du visible. Citons comme exemple de couche fonctionnelle antisolaire, les produits commercialisés sous le nom de « Stopray » par la société AGC et comme exemple de revêtement bas émissif les produits commercialisé sous le terme « TopN, TopN+, TopN+T » par la même société. Thus, the invention is based on a completely new and inventive approach to passivation of the functional layer, the inventors having determined that surprisingly the presence of a sulfur compound at the extreme surface allows such passivation. By the term "presence of an sulfur compound at the extreme surface" is meant a sulfur content expressed as an atomic percentage of at least 0.4% over a thickness of 10 nm, said percentage being measured by spectroscopy of XPS electron photo. The support on which the functional layer is deposited is preferably rigid. The function of the support is to support and / or protect the functional layer. According to a particular embodiment, the support comprises at least a total or partial structuring surface on at least one of its faces. Generally, the structuring of the support comprises at least one of the processes selected from etching, rolling and / or laser etching. The chemical etching of the support comprises at least the matting and / or etching (for example by etching with hydrofluoric acid of a silicosodocalcic glass). The rolling method comprises at least the step of structuring the substrate by the pressure impression of a pattern using at least one printing roll. The substrate may be glass, rigid plastics material (eg organic glass, polycarbonate) or flexible polymeric films (eg polyvinyl butyral (PVB), polyethylene terephthalate (PET), vinyl acetate copolymer and ethylene (EVA)). Preferably the support is a glass sheet. The glasses are mineral or organic. The mineral glasses are preferred. Among these, the clear or colored silicosodocalcic glasses are preferred in the mass or on the surface. More preferably, they are extra clear silicosodocalcic glasses. The term extra clear means a glass containing at most 0.020% by weight of the total Fe glass expressed in Fe 2 0 3 and preferably at most 0.015% by weight. The support preferably has a geometric thickness of at least 0.35 mm. By the terms "geometrical thickness", one understands the average physical thickness. By the term "layer" in the sense of the present invention, it is meant that said layer may consist of a layer of single material or a plurality of layers each of a different material. The functional layer may thus be an electrical conduction layer comprising at least one metal layer based on silver, the silver being present in pure form or alloyed with another metal, the pure form being preferred. When the electrical conduction functional layer comprises at least one silver-based metal layer, said silver-based metal layer is protected on both sides by at least one oxide or nitride-based layer. When the silver is present in allied form, the other metal preferably comprises at least palladium and / or gold, more preferably palladium. When the layer functional is a functional layer of electrical conduction comprising at least one metal layer based on silver, said layer also comprises a set of dielectric layers disposed on either side of said silver-based metal layer. The silver-based metal layer has a geometric thickness of at least 5.0 nm, preferably at least 9.0 nm. The silver-based metal layer has a geometric thickness of at most 25.0 nm, preferably at most 18.0 nm, more preferably at most 14.0 nm. Most preferably, the metal layer based on silver has a thickness equal to 12.5 nm. The electrical conductivity layer may comprise several silver-based metal layers, preferably two silver-based metal layers, said layers being separated by dielectric layers making the support covered with a functional layer according to the invention. Reflective in a part of the spectrum of solar radiation, in particular in the field of visible lengths. As an example of a sunscreen functional layer, the products marketed under the name of "Stopray" by the company AGC and as an example of low-emitting coating products marketed under the term "TopN, TopN +, TopN + T" by the same company.
Selon un mode de réalisation, la couche fonctionnelle de conduction électrique, basse émissive ou antisolaire comprenant au moins une couche métallique à base d'argent comprend également au moins un moyen de protection chimique de ladite couche d'argent. Par les termes « protection chimique », on entend désigner une protection contre tout phénomène de dégradation chimique de l'argent (oxydation, diffusion d'ions alcalins provenant de la feuille de verre, diffusion de l'argent lors du traitement thermique de trempe). Parmi ces moyens, citons pour exemple : According to one embodiment, the functional electric conduction layer, low emissive or antisolar comprising at least one silver-based metal layer also comprises at least one means of chemical protection of said silver layer. The term "chemical protection" is intended to denote protection against any phenomenon of chemical degradation of silver (oxidation, diffusion of alkaline ions from the glass sheet, diffusion of silver during quenching heat treatment) . Among these means, for example:
• au moins une couche barrière, ladite couche barrière étant, par rapport à la feuille de verre la première couche constituant la couche fonctionnelle de conduction électrique, basse émissive ou antisolaire. Le matériau constituant la couche barrière étant sélectionné parmi
l'oxyde de titane, l'oxyde de zinc, le nitrure de silicium, l'oxynitrure de silicium, l'oxycarbure de silicium, l'oxycarbonitrure de silicium, le nitrure d'aluminium, l'oxynitrure d'aluminium, l'oxyde d'aluminium, cette couche barrière étant éventuellement dopée ou alliée à l'étain. La couche barrière a une épaisseur géométrique d'au moins 3,0 nm, de préférence d'au moins 10,0 nm, plus préférentiellement d'au moins 30,0 nm, encore plus préférentiellement d'au moins 50,0 nm. La couche barrière a une épaisseur d'au plus 100 nm. At least one barrier layer, said barrier layer being, with respect to the glass sheet, the first layer constituting the functional layer of electrical conduction, low emissive or antisolar. The material constituting the barrier layer being selected from titanium oxide, zinc oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum nitride, aluminum oxynitride, aluminum oxide, this barrier layer being optionally doped or alloyed with tin. The barrier layer has a geometric thickness of at least 3.0 nm, preferably at least 10.0 nm, more preferably at least 30.0 nm, even more preferably at least 50.0 nm. The barrier layer has a thickness of at most 100 nm.
• au moins une couche sacrificielle, la couche sacrificielle étant située sur au moins une face de la couche métallique à base d'argent. Par couche sacrificielle, on entend une couche pouvant être oxydée en tout ou partie. Cette couche permet d'éviter une détérioration de la couche d'argent, notamment par oxydation. Lorsqu'elle est présente, la couche sacrificielle comprend au moins un composé choisi parmi les métaux, les nitrures, les oxydes, les oxydes métalliques sous-stoechiométriques en oxygène. Préférentiellement, les métaux, nitrures, oxydes, oxydes métalliques sous-stoechiométriques comprennent au moins un élément sélectionné parmi le Ti, le Zr, l'Hf, le V, le Nb, le Ta, le Cr, le Mo, le W, le Mn, le Fe, le Co, le Ni, le Cu, Zn, l'Ai. Plus préférentiellement, la couche sacrificielle comprend au moins le Ti, le TiOx (avec x < 2) ou le NiCr. L'épaisseur de la couche sacrificielle est d'au moins 0,5 nm. L'épaisseur de la couche sacrificielle est d'au plus 6,0 nm, Plus préférentiellement, l'épaisseur se situe entre 1,0 et 2,5 nm. Selon un mode préféré de réalisation, une couche sacrificielle est déposée sur la face de la couche métallique à base d'argent la plus éloignée par rapport au support. At least one sacrificial layer, the sacrificial layer being located on at least one face of the silver-based metal layer. By sacrificial layer is meant a layer that can be oxidized in whole or in part. This layer makes it possible to avoid deterioration of the silver layer, in particular by oxidation. When present, the sacrificial layer comprises at least one compound chosen from metals, nitrides, oxides and sub-stoichiometric oxygen oxides. Preferably, the metals, nitrides, oxides and sub-stoichiometric metal oxides comprise at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al. More preferably, the sacrificial layer comprises at least Ti, TiO x (with x <2) or NiCr. The thickness of the sacrificial layer is at least 0.5 nm. The thickness of the sacrificial layer is at most 6.0 nm. More preferably, the thickness is between 1.0 and 2.5 nm. According to a preferred embodiment, a sacrificial layer is deposited on the face of the silver metal layer furthest away from the support.
Selon un mode de réalisation préféré, le substrat selon l'invention est tel que la couche fonctionnelle de conduction électrique comprend une couche mince d'uniformisation des propriétés électriques de surface, ladite couche d'uniformisation étant la couche la plus éloignée du support au sein de la couche
fonctionnelle. La couche d'uniformisation a pour fonction principale de permettre l'obtention d'un transfert uniforme de charge sur toute la surface de la couche fonctionnelle. Ce transfert uniforme se traduit, lorsque la couche fonctionnelle conductrice est utilisée en tant qu'électrode dans un dispositif OLED, par un flux de lumière émise ou convertie équivalente en tout point de la surface. Il permet également d'augmenter la durée de vie des dispositifs optoélectroniques étant donné que ce transfert est le même en chaque point, éliminant de la sorte de possibles points chauds. La couche d'uniformisation a une épaisseur géométrique d'au moins 0,5 nm, préférentiellement d' au moins 1 ,0 nm. La couche d'uniformi s ation a une ép ai s s eur g éométri que d ' au p lus 5 , 0 nm , préférentiellement d'au plus 2,5 nm, plus préférentiellement d'au plus 2,0 nm. Plus préférentiellement, la couche d'uniformisation est égale à 1,5 nm. La couche d'uniformisation comprend au moins une couche comprenant au moins un matériau inorganique sélectionné parmi un métal, un nitrure, un oxyde, un carbure, un oxynitrure, un oxycarbure, un carbonitrure, un oxycarbonitrure ainsi que les mélanges d'au moins deux d'entre eux. According to a preferred embodiment, the substrate according to the invention is such that the functional layer of electrical conduction comprises a thin layer of uniformity of the surface electrical properties, said uniformization layer being the furthest layer of the support within of the diaper functional. The main function of the uniformization layer is to obtain a uniform charge transfer over the entire surface of the functional layer. This uniform transfer results, when the conductive functional layer is used as an electrode in an OLED device, by an equivalent emitted or converted light flux at any point on the surface. It also increases the life of optoelectronic devices since this transfer is the same at each point, eliminating possible hot spots. The uniformization layer has a geometric thickness of at least 0.5 nm, preferably at least 1.0 nm. The uniformity layer has an angular frequency of at most 5.0 nm, preferably at most 2.5 nm, more preferably at most 2.0 nm. More preferably, the uniformization layer is equal to 1.5 nm. The uniformization layer comprises at least one layer comprising at least one inorganic material selected from a metal, a nitride, an oxide, a carbide, an oxynitride, an oxycarbide, a carbonitride, an oxycarbonitride and the mixtures of at least two of them.
Selon un premier mode particulier de réalisation du mode précédent, le matériau inorganique de la couche d'uniformisation comprend un métal seul ou un mélange de métaux. L'expression générique « mélange de métaux » désigne les combinaisons d'au moins deux métaux sous la forme d'alliage ou d'un dopage d'au moins un métal par au moins un autre métal. La couche d'uniformisation comprend au moins ceux appartenant aux colonnes 1 , 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 du tableau de la classification périodique des éléments dans sa version publiée par l'IUPAC, le 22 juin 2007. Le métal et/ou le mélange de métaux comprend au moins un élément sélectionné parmi Li, Na, K, Rb, Mg, Ca, Sr, Ba, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si, C. Plus préférentiellement, le métal ou le mélange de métaux comprend au moins un élément sélectionné parmi C, Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, Zn. Le mélange de métaux comprend préférentiellement Ni-Cr et/ou Zn dopé à l'Ai. L'avantage offert par ce mode de réalisation particulier est qu'il permet
d'obtenir le meilleur compromis possible entre, d'une part, les propriétés électriques résultant de l'effet de la couche d'uniformisation des propriétés électriques de surface et, d'autre part, les propriétés optiques obtenues grâce à la couche d'optimisation optique. L'utilisation d'une couche d'uniformisation ayant une épaisseur la plus faible possible est fondamentale. En effet, l'influence de cette couche sur la quantité de lumière émise ou convertie par le dispositif optoélectronique est d'autant plus faible que son épaisseur est faible. According to a first particular embodiment of the preceding mode, the inorganic material of the uniformization layer comprises a single metal or a mixture of metals. The generic term "metal mixture" refers to combinations of two or more metals in the form of an alloy or a doping of at least one metal with at least one other metal. The uniformization layer comprises at least those belonging to columns 1, 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 of the table of the periodic table of elements in its version published by IUPAC, June 22, 2007. The metal and / or metal mixture comprises at least one element selected from Li, Na, K, Rb, Mg, Ca, Sr, Ba, Ti, Zr, Hf, V, Nb. , Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si, C. More preferably, the metal or the mixture of metals comprises at least one element selected from C, Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, Zn. The metal mixture preferably comprises Ni-Cr and / or Zn doped with Al. The advantage offered by this particular embodiment is that it allows to obtain the best possible compromise between, on the one hand, the electrical properties resulting from the effect of the uniformity layer of the surface electrical properties and, on the other hand, the optical properties obtained thanks to the layer of optical optimization. The use of a uniformization layer having the lowest possible thickness is fundamental. Indeed, the influence of this layer on the amount of light emitted or converted by the optoelectronic device is even lower than its thickness is low.
Selon un second mode particulier de réalisation, le matériau inorganique de la couche d'uniformisation est présent sous la forme d'au moins un composé chimique sélectionné parmi les carbures, les carbonitrures, les oxynitrures, les oxycarbures, les oxycarbonitrures ainsi que les mélanges d'au moins deux d'entre eux. Les oxynitrures, oxycarbures, oxycarbonitrures de la couche d'uniformisation peuvent être sous forme non-stoechiométrique, de préférence sous-stoechiométrique par rapport à l'oxygène. Les carbures, les carbonitrures, oxynitrures, oxycarbures, oxycarbonitrures sont des carbures, carbonitrures, oxynitrures, oxycarbures, oxycarbonitrures d'au moins un élément sélectionné parmi ceux appartenant aux colonnes 2, 4, 6, 7, 8, 9, 10, 11 , 12, 13, 14 du tableau de la classification périodique des éléments dans sa version publiée par l'IUPAC, le 22 juin 2007. Préférentiellement, ce sont des carbures, carbonitrures, oxynitrures, oxycarbures, oxycarbonitrures d'au moins un élément sélectionné parmi Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si. Plus préférentiellement, ce sont des carbures, carbonitrures, oxynitrures, oxycarbures, oxycarbonitrures d'au moins un élément sélectionné parmi Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, Zn. Les carbures, carbonitrures, oxynitrures, oxycarbures, oxycarbonitrures de la couche d'uniformisation des propriétés électriques de surface comprennent éventuellement au moins un élément dopant. Dans un mode de réalisation préféré, la couche mince d'uniformisation comprend au moins un oxynitrure comprenant au moins un élément sélectionné parmi Ti, Zr, Cr, Mo , W, Mn, Co , Ni , Pd, Pt, Cu, Ag , Au, Zn, C d, Al, S i . P lus préférentiellement, la couche mince d'uniformisation des propriétés électrique de
surface comprend au moins un oxynitrure choisi parmi l'oxynitrure de Ti, l'oxynitrure de Zr, l'oxynitrure de Ni, l'oxynitrure de NiCr. According to a second particular embodiment, the inorganic material of the uniformization layer is present in the form of at least one chemical compound selected from carbides, carbonitrides, oxynitrides, oxycarbides, oxycarbonitrides and mixtures of at least two of them. The oxynitrides, oxycarbides and oxycarbonitrides of the uniformization layer may be in non-stoichiometric form, preferably substoichiometric with respect to oxygen. Carbides, carbonitrides, oxynitrides, oxycarbides and oxycarbonitrides are carbides, carbonitrides, oxynitrides, oxycarbides and oxycarbonitrides of at least one element selected from those belonging to columns 2, 4, 6, 7, 8, 9, 10, 11, 12, 13, 14 of the table of the periodic table of the elements in its version published by IUPAC, on June 22, 2007. Preferably, these are carbides, carbonitrides, oxynitrides, oxycarbures, oxycarbonitrides of at least one element selected from Ti , Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si. More preferably, they are carbides, carbonitrides oxynitrides, oxycarbides, oxycarbonitrides of at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, Zn. The carbides, carbonitrides, oxynitrides, oxycarbides and oxycarbonitrides of the uniformity layer of the surface electrical properties optionally comprise at least one doping element. In a preferred embodiment, the uniformizing thin film comprises at least one oxynitride comprising at least one element selected from Ti, Zr, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au. , Zn, C d, Al, S i. More preferentially, the thin film of uniformity of the electrical properties of surface comprises at least one oxynitride selected from Ti oxynitride, Zr oxynitride, Ni oxynitride, NiCr oxynitride.
Selon un troisième mode particulier de réalisation, le matériau inorganique de la couche d'uniformisation est présent sous la forme d'au moins un nitrure métallique d'au moins un élément sélectionné parmi ceux appartenant aux colonnes 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14 du tableau de la classification périodique des éléments dans sa version publiée par l'IUPAC, le 22 juin 2007. Préférentiellement, la couche d'uniformisation comprend au moins un nitrure d'un élément sélectionné parmi Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si. Plus préférentiellement, le nitrure comprend au moins un élément sélectionné parmi Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, Zn. Plus préférentiellement, la couche mince d'uniformisation des propriétés électriques de surface comprend au moins le nitrure de Ti, le nitrure de Zr, le nitrure de Ni, le nitrure de NiCr. Selon un quatrième mode particulier de réalisation, le matériau inorganique de la couche d'uniformisation est présent sous la forme d'au moins un oxyde métallique d'au moins un élément sélectionné parmi ceux appartenant aux colonnes 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14 du tableau de la classification périodique des éléments dans sa version publiée par l'IUPAC, le 22 juin 2007. Préférentiellement, la couche d'uniformisation comprend au moins un oxyde d'un élément sélectionné parmi Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, In, Si, Sn. Plus préférentiellement, l'oxyde comprend au moins un élément sélectionné parmi Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, In, Sn, Zn. L'oxyde de la couche d'uniformisation peut être un oxyde sous stoechiométrique en oxygène. L'oxyde comprend éventuellement au moins un élément dopant. De préférence, l'élément dopant est sélectionné parmi au moins un des éléments choisis parmi l'Ai, le Ga, l'In, le Sn, le Sb, le F. Plus préférentiellement, la couche mince d'uniformisation des propriétés électrique de surface comprend au moins l'oxyde de Ti et/ou l'oxyde de Zr et/ou l'oxyde de Ni et/ou l'oxyde de NiCr et/ou ΓΙΤΟ et/ou l'oxyde de Sn dopé, le dopant étant au moins un élément choisi parmi
le F et le Sb, et/ou l'oxyde de Zn dopé, le dopant étant au moins un élément choisi parmi l'Ai, le Ga, le Sn, le Ti. According to a third particular embodiment, the inorganic material of the uniformization layer is present in the form of at least one metal nitride of at least one element selected from those belonging to columns 4, 5, 6, 7, 8 , 9, 10, 1 1, 12, 13, 14 of the table of the periodic table of elements in its version published by IUPAC, on June 22, 2007. Preferably, the standardization layer comprises at least one nitride of a element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si. More preferably, the nitride comprises at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, Zn. More preferably, the thin film of uniformity of the surface electrical properties comprises at least Ti nitride, Zr nitride, Ni nitride, NiCr nitride. According to a fourth particular embodiment, the inorganic material of the uniformization layer is present in the form of at least one metal oxide of at least one element selected from those belonging to columns 4, 5, 6, 7, 8 , 9, 10, 1 1, 12, 13, 14 of the table of the periodic table of elements in its version published by IUPAC, on June 22, 2007. Preferably, the uniformization layer comprises at least one oxide of a element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, In, Si, Sn. More preferably, the oxide comprises at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, In, Sn, Zn. The oxide of the uniformization layer may be an oxide under stoichiometric oxygen. The oxide optionally comprises at least one doping element. Preferably, the doping element is selected from at least one of the elements selected from Al, Ga, In, Sn, Sb, and F. More preferably, the thin film of uniformity of the electrical properties of surface comprises at least the Ti oxide and / or the Zr oxide and / or the Ni oxide and / or the NiCr oxide and / or ΓΙΤΟ and / or the doped Sn oxide, the dopant being at least one element selected from F and Sb, and / or doped Zn oxide, the dopant being at least one element selected from Al, Ga, Sn, Ti.
Selon un mode de réalisation préféré, le substrat selon l'invention est tel que la couche fonctionnelle de conduction électrique comprend une couche insérée entre la couche métallique à base d'argent et la couche d'uniformisation comprenant au moins un composé chimique inorganique. Cette couche d'insertion a pour fonction de constituer une partie d'une cavité optique permettant de rendre la couche métallique à base d'argent transparente. Le terme composé chimique inorganique comprend au moins un composé diélectrique et/ou au moins un composé conducteur de l'électricité. Le composé diélectrique comprend au moins un composé choisi parmi les oxydes, les nitrures, les carbures, les oxynitrures, les oxycarbures, les carbonitrures, les oxycarbonitrures ainsi que les mélanges d'au moins deux d'entre eux. Les oxydes, nitrures, carbures, oxynitrures, oxycarbures, carbonitrures ou oxycarbonitrures du composé diélectrique sont des oxydes, nitrures, carbures, oxynitrures, oxycarbures, carbonitrures ou oxycarbonitrures d'au moins un élément sélectionné parmi le Ti, le Zr, le Hf, le Ta, le Cr, le Mo, le Zn, l'Ai, l'In, le Si, le Sn, le Sb, le Bi. Lorsqu'il est présent, le composé diélectrique comprend de préférence un oxyde de titane, un oxyde de zinc, un oxyde d'étain, un nitrure d'aluminium, un nitrure de silicium et/ou un carbure de silicium. Lorsqu'il est présent, le conducteur comprend au moins un composé choisi parmi les oxydes sous stoechiométriques en oxygène, les oxydes dopés, les nitrures dopés, les carbures dopés, les oxynitrures dopés, les oxycarbures dopés, les carbonitrures dopés, les oxycarbonitrures dopés ainsi que les mélanges d'au moins deux d'entre eux. Les oxydes sous stoechiométriques, oxydes dopés, nitrures dopés, carbures dopés, oxynitrures dopés, oxycarbures dopés, carbonitrures dopés ou oxycarbonitrures dopés du composé conducteur sont des oxydes sous stoechiométriques, des oxydes dopés, des nitrures dopés, des carbures dopés, des oxynitrures dopés, des oxycarbures dopés, des carbonitrures dopés ou des oxycarbonitrures dopés d'au moins un élément sélectionné parmi le Ti, le Zr, le Ta, le Cr, le Mo, le Zn, l'Ai, l'In, le Si , le Sn, le Sb .
Préférentiellement, les dopants comprennent au moins un des éléments choisis parmi l'Ai, le Ga, l'In, le Sn, le P, le Sb, le F. Plus préférentiellement le composé conducteur comprend au moins ΓΙΤΟ et/ou l'oxyde de Sn dopé, le dopant étant au moins un élément choisi parmi le F et le Sb, et/ou l'oxyde de Zn dopé, le dopant étant au moins un élément choisi parmi l'Ai, le Ga, le Sn, le Ti. Selon un mode préféré de réalisation, le composé chimique inorganique comprend au moins du ZnOx (avec x < 1) et/ou ZnxSnyOz (avec x + y > 3 et z < 6). Préférentiellement, le ZnxSnyOz comprend au plus 95% en poids de zinc, le pourcentage en poids de zinc est exprimé par rapport au poids total des métaux présents dans la couche. La couche d'insertion a une épaisseur géométrique d'au moins 3,0 nm. La couche d'insertion a une épaisseur géométrique d'au plus 50,0 nm, de préférence d'au plus 20,0 nm, plus préférentiellement d'au plus 10,0 nm. According to a preferred embodiment, the substrate according to the invention is such that the electrical conduction functional layer comprises a layer inserted between the silver-based metal layer and the uniformization layer comprising at least one inorganic chemical compound. This insertion layer has the function of forming part of an optical cavity making it possible to make the metal layer based on transparent silver. The term inorganic chemical compound comprises at least one dielectric compound and / or at least one electrically conductive compound. The dielectric compound comprises at least one compound chosen from oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides and mixtures of at least two of them. The oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides or oxycarbonitrides of the dielectric compound are oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides or oxycarbonitrides of at least one element selected from Ti, Zr, Hf, Ta, Cr, Mo, Zn, Ai, In, Si, Sn, Sb, Bi. When present, the dielectric compound preferably comprises a titanium oxide, a zinc oxide, a tin oxide, an aluminum nitride, a silicon nitride and / or a silicon carbide. When present, the conductor comprises at least one compound chosen from oxides in stoichiometric oxygen, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides, doped oxycarbonitrides and than the mixtures of at least two of them. The stoichiometric oxides, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides or doped oxycarbonitrides of the conducting compound are sub stoichiometric oxides, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides or doped oxycarbonitrides of at least one element selected from Ti, Zr, Ta, Cr, Mo, Zn, Al, In, Si, Sn , the Sb. Preferably, the dopants comprise at least one of the elements chosen from Al, Ga, In, Sn, P, Sb and F. More preferably, the conducting compound comprises at least ΓΙΤΟ and / or oxide. doped Sn, the dopant being at least one element selected from F and Sb, and / or doped Zn oxide, the dopant being at least one element selected from A 1, Ga, Sn, Ti . According to a preferred embodiment, the inorganic chemical compound comprises at least ZnO x (with x <1) and / or Zn x Sn y O z (with x + y> 3 and z <6). Preferably, the Zn x Sn y O z comprises at most 95% by weight of zinc, the weight percentage of zinc is expressed relative to the total weight of the metals present in the layer. The insertion layer has a geometric thickness of at least 3.0 nm. The insertion layer has a geometric thickness of at most 50.0 nm, preferably at most 20.0 nm, more preferably at most 10.0 nm.
Selon un mode particulier de réalisation, le substrat selon l'invention est tel que la couche fonctionnelle de conduction électrique comprend au moins une couche d'optimisation optique insérée entre la couche métallique à base d'argent et le support. Cette couche d'optimisation permet, grâce à son épaisseur et sa nature chimique, d'obtenir un flux de lumière élevée. Elle comprend au moins un composé chimique inorganique. Le terme composé chimique inorganique comprend au moins un composé diélectrique et/ou au moins un composé conducteur de l'électricité. Le composé diélectrique comprend au moins un composé choisi parmi les oxydes, les nitrures, les carbures, les oxynitrures, les oxycarbures, les carbonitrures, les oxycarbonitrures ainsi que les mélanges d' au moins deux d' entre eux. Les oxydes, nitrures, carbures, oxynitrures, oxycarbures, carbonitrures ou oxycarbonitrures du composé diélectrique sont des oxydes, nitrures, carbures, oxynitrures, oxycarbures, carbonitrures ou oxycarbonitrures d'au moins un élément sélectionné parmi le Ti, le Zr, le Hf, le Nb, le Ta, le Cr, le Mo, le Zn, l'Ai, l'In, le Si, le Sn, le Sb, le Bi. Lorsqu'il est présent, le composé diélectrique comprend de préférence un oxyde de titane, un oxyde de zirconium, un oxyde d'hafnium, un oxyde de niobium, un oxyde de tantale, un oxyde de zinc, un nitrure d'aluminium, un nitrure de silicium
et/ou un carbure de silicium. Lorsqu'il est présent, le conducteur comprend au moins un composé choisi parmi les oxydes sous stoechiométriques en oxygène, les oxydes dopés, les nitrures dopés, les carbures dopés, les oxynitrures dopés, les oxycarbures dopés, les carbonitrures dopés, les oxycarbonitrures dopés ainsi que les mélanges d'au moins deux d'entre eux. Les oxydes sous stoechiométriques, oxydes dopés, nitrures dopés, carbures dopés, oxynitrures dopés, oxycarbures dopés, carbonitrures dopés ou oxycarbonitrures dopés du composé conducteur sont des oxydes sous stoechiométriques, des oxydes dopés, des nitrures dopés, des carbures dopés, des oxynitrures dopés, des oxycarbures dopés, des carbonitrures dopés ou des oxycarbonitrures dopés d'au moins un élément sélectionné parmi le Ti, le Zr, le Ta, le Cr, le Mo, le Zn, l 'Ai, l'In, le Si, le Sn, le P, le Sb . Préférentiellement, les dopants comprennent au moins un des éléments choisis parmi l'Ai, le Ga, l'In, le Sn, le Sb, le F. Plus préférentiellement le composé conducteur comprend au moins TITO et/ou l'oxyde de Sn dopé, le dopant étant au moins un élément choisi parmi le F et le Sb, et/ou l'oxyde de Zn dopé, le dopant étant au moins un élément choisi parmi l'Ai, le Ga, le Sn, le Ti. Selon un mode préféré de réalisation, le composé chimique inorganique comprend au moins du ZnOx (avec x < 1) et/ou ZnxSnyOz (avec x + y > 3 et z < 6). Préférentiellement, le ZnxSnyOz comprend au plus 95% en poids de zinc, le pourcentage en poids de zinc est exprimé par rapport au poids total des métaux présents dans la couche. La couche d'optimisation optique a une épaisseur géométrique d'au moins 3,0 nm, de préférence d'au moins 10,0 nm, plus préférentiellement d'au moins 30,0 nm, encore plus préférentiellement d'au moins 50,0 nm. La couche d'optimisation optique a une épaisseur d'au plus 100 nm. Selon un mode particulier de réalisation le substrat selon l'invention est tel que la couche fonctionnelle de conduction électrique comprend au moins une couche supplémentaire de cristallisation insérée entre le support et la couche métallique à base d'argent. Cette couche permet une croissance préférentielle de la couche métallique à base d'argent et permet d'obtenir de ce fait de bonnes propriétés électriques et optiques de ladite couche. Elle comprend
au moins un composé chimique inorganique. Le terme composé chimique inorganique comprend au moins au moins du ZnOx (avec x < 1) et/ou ZnxSnyOz (avec x + y > 3 et z < 6). Préférentiellement, le ZnxSnyOz comprend au plus 95% en poids de zinc, le pourcentage en poids de zinc est exprimé par rapport au poids total des métaux présents dans la couche. La couche de cristallisation a une épaisseur géométrique d'au moins 3,0 nm. La couche de cristallisation a une épaisseur d'au plus 50,0 nm, de préférence d'au plus 20,0 nm, plus préférentiellement d'au plus 10,0 nm. Selon un mode particulier de réalisation, la couche de cristallisation est confondue avec la couche barrière et/ou la couche d'optimisation optique. According to a particular embodiment, the substrate according to the invention is such that the electrical conduction functional layer comprises at least one optical optimization layer inserted between the silver-based metal layer and the support. This optimization layer makes it possible, thanks to its thickness and its chemical nature, to obtain a high light flux. It comprises at least one inorganic chemical compound. The term inorganic chemical compound comprises at least one dielectric compound and / or at least one electrically conductive compound. The dielectric compound comprises at least one compound chosen from oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides and mixtures of at least two of them. The oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides or oxycarbonitrides of the dielectric compound are oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides or oxycarbonitrides of at least one element selected from Ti, Zr, Hf, Nb, Ta, Cr, Mo, Zn, Ai, In, Si, Sn, Sb, Bi. When present, the dielectric compound preferably comprises a titanium oxide, a zirconium oxide, a hafnium oxide, a niobium oxide, a tantalum oxide, a zinc oxide, an aluminum nitride, a silicon nitride and / or silicon carbide. When present, the conductor comprises at least one compound chosen from oxides in stoichiometric oxygen, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides, doped oxycarbonitrides and than the mixtures of at least two of them. The stoichiometric oxides, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides or doped oxycarbonitrides of the conducting compound are sub stoichiometric oxides, doped oxides, doped nitrides, doped carbides, doped oxynitrides, doped oxycarbides, doped carbonitrides or doped oxycarbonitrides of at least one element selected from Ti, Zr, Ta, Cr, Mo, Zn, Al, In, Si, Sn , the P, the Sb. Preferably, the dopants comprise at least one of the elements chosen from Al, Ga, In, Sn, Sb and F. More preferentially, the conducting compound comprises at least TITO and / or doped Sn oxide. , the dopant being at least one element selected from F and Sb, and / or doped Zn oxide, the dopant being at least one element selected from Al, Ga, Sn, Ti. According to a preferred embodiment, the inorganic chemical compound comprises at least ZnO x (with x <1) and / or Zn x Sn y O z (with x + y> 3 and z <6). Preferably, the Zn x Sn y O z comprises at most 95% by weight of zinc, the weight percentage of zinc is expressed relative to the total weight of the metals present in the layer. The optical optimization layer has a geometric thickness of at least 3.0 nm, preferably at least 10.0 nm, more preferably at least 30.0 nm, even more preferably at least 50, 0 nm. The optical optimization layer has a thickness of at most 100 nm. According to a particular embodiment, the substrate according to the invention is such that the electrical conduction functional layer comprises at least one additional crystallization layer inserted between the support and the silver-based metal layer. This layer allows a preferential growth of the silver-based metal layer and thus makes it possible to obtain good electrical and optical properties of said layer. She understands at least one inorganic chemical compound. The term inorganic chemical compound comprises at least at least ZnO x (with x <1) and / or Zn x Sn y O z (with x + y> 3 and z <6). Preferably, the Zn x Sn y O z comprises at most 95% by weight of zinc, the weight percentage of zinc is expressed relative to the total weight of the metals present in the layer. The crystallization layer has a geometric thickness of at least 3.0 nm. The crystallization layer has a thickness of at most 50.0 nm, preferably at most 20.0 nm, more preferably at most 10.0 nm. According to one particular embodiment, the crystallization layer is merged with the barrier layer and / or the optical optimization layer.
Selon un autre mode préféré de réalisation, la somme des épaisseurs géométriques des couches barrière, d'optimisation optique et de cristallisation est d'au moins 3,0 nm, de préférence d'au moins 10,0 nm, plus préférentiellement d'au moins 30,0 nm, encore plus préférentiellement d'au moins 50,0 nm. Préférentiellement, la somme des épaisseurs des couches a au plus 100 nm. According to another preferred embodiment, the sum of the geometric thicknesses of the barrier, optical optimization and crystallization layers is at least 3.0 nm, preferably at least 10.0 nm, more preferably from minus 30.0 nm, still more preferably at least 50.0 nm. Preferably, the sum of the thicknesses of the layers has at most 100 nm.
Selon un mode préféré de réalisation des couches barrière et de cristallisation, au moins une de ces deux couches est confondue avec la couche d'optimisation optique. According to a preferred embodiment of the barrier and crystallization layers, at least one of these two layers is merged with the optical optimization layer.
Les couches barrière, d'optimisation, de cristallisation et d'insertion peuvent être de même nature chimique ou de nature chimique différente. Les termes « nature chimique différente » n'excluent pas la possibilité de combinaisons de type : 3 couches de nature identique et une de nature différente ou encore deux couches de nature identique, les deux couches restantes étant indifféremment de nature identique entre-elles ou de nature différente. The barrier, optimization, crystallization and insertion layers may be of the same chemical nature or of a different chemical nature. The terms "different chemical nature" do not exclude the possibility of combinations of type: 3 layers of identical nature and one of a different nature or two layers of identical nature, the two remaining layers being indifferently identical in nature to each other or to different nature.
Selon un autre mode particulier de réalisation, le substrat selon l'invention est tel qu'il comprend entre le support et la couche d'uniformisation, au moins un empilement supplémentaire: couche métallique à base d'argent, couche d'insertion. Cet empilement peut être reproduit n fois, avec n représentant
un nombre entier supérieur ou égal à 1. L'empilement constituant la couche fonctionnelle de conduction électrique est, de préférence, un empilement comprenant de une à trois couches métalliques à base d'argent, préférentiellement une ou deux couches métalliques à base d'argent . Selon un mode de réalisation préféré, le substrat selon l'invention présente essentiellement la structure suivante à partir du support : According to another particular embodiment, the substrate according to the invention is such that it comprises between the support and the uniformization layer, at least one additional stack: silver-based metal layer, insertion layer. This stack can be reproduced n times, with n representing an integer greater than or equal to 1. The stack constituting the functional electrical conduction layer is preferably a stack comprising from one to three silver-based metal layers, preferably one or two silver-based metal layers. . According to a preferred embodiment, the substrate according to the invention essentially has the following structure from the support:
Couche barrière et couche d'optimisation optique confondues: épaisseur 50-80 nm en Ti02 ; Barrier layer and optical optimization layer combined: thickness 50-80 nm in Ti0 2 ;
• Couche de cristallisation : épaisseur 3-20 nm en ZnxSnyOz tel que défini précédemment • Crystallization layer: thickness 3-20 nm in Zn x Sn y O z as previously defined
• Couche métallique à base d'argent: épaisseur 8-14nm en Ag pur • Silver-based metal layer: 8-14nm thick in pure Ag
• Couche sacrificielle : épaisseur 1-3 nm en Ti • Sacrificial layer: thickness 1-3 nm in Ti
• Couche d'insertion: épaisseur 3-20nm en ZnxSnyOz tel que défini précédemment • Insertion layer: thickness 3-20nm in Zn x Sn y O z as previously defined
• Couche d'uniformisation : épaisseur 0.5-3 nm en X avec X : Li, Mg, Cu, Ti, Zr, Hf, V, Nb, Ta, Ni, Pd, Cr, Mo, Al, Zn, Ni-Cr ou Zn dopé à l'Ai, en nitrure de X avec X : Ti, Zr, Hf, V, Nb, Ta, Ni, Pd, Cr, Mo, Al, Zn, Ni-Cr, en oxynitrure de X avec X : Ti, Zr, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si ou de NiCr, en oxyde de X avec X : Ti, Zr, Hf, V, Nb, Ta, Ni, Pd, Cr, Mo, Al, Zn, Ni-Cr ou Zn dopé à l'Ai. • Standardization layer: thickness 0.5-3 nm in X with X: Li, Mg, Cu, Ti, Zr, Hf, V, Nb, Ta, Ni, Pd, Cr, Mo, Al, Zn, Ni-Cr or Zn doped with Al, in nitride of X with X: Ti, Zr, Hf, V, Nb, Ta, Ni, Pd, Cr, Mo, Al, Zn, Ni-Cr, in oxynitride of X with X: Ti , Zr, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si or NiCr, to X oxide with X: Ti, Zr, Hf, V , Nb, Ta, Ni, Pd, Cr, Mo, Al, Zn, Ni-Cr or Zn doped with Al.
Selon un mode de réalisation particulier, le substrat selon l'invention est tel que la couche fonctionnelle est une couche discontinue sous forme de zones adjacentes distinctes, notamment sous forme de bandes parallèles.
Selon un mode de réalisation avantageux, le substrat selon l'invention est tel que ladite couche fonctionnelle discontinue présente une variation d'épaisseur du milieu de zone aux bords de zone de moins de 30%, préférentiellement de moins de 15%, le plus préférentiellement de moins de 5%, le plus avantageusement de moins de 1%. According to a particular embodiment, the substrate according to the invention is such that the functional layer is a discontinuous layer in the form of distinct adjacent zones, in particular in the form of parallel strips. According to an advantageous embodiment, the substrate according to the invention is such that said discontinuous functional layer exhibits a thickness variation of the zone medium at the zone edges of less than 30%, preferably less than 15%, most preferably less than 5%, most preferably less than 1%.
Selon un mode préférentiel de réalisation, le substrat selon l'invention est une anode pour dispositifs optoélectroniques, de manière plus préférée pour un dispositif organique électroluminescent (OLED). According to a preferred embodiment, the substrate according to the invention is an anode for optoelectronic devices, more preferably for an organic electroluminescent device (OLED).
Un autre objet de l'invention concerne le procédé de fabrication d'un substrat muni d'une couche fonctionnelle selon l'invention. Selon une première mise en œuvre avantageuse, l'invention concerne un procédé de passivation de la surface d'un substrat muni d'une couche fonctionnelle tel qu'il comprend les étapes successives suivantes : Another subject of the invention concerns the process for manufacturing a substrate provided with a functional layer according to the invention. According to a first advantageous implementation, the invention relates to a method of passivating the surface of a substrate provided with a functional layer such that it comprises the following successive stages:
• Etape de dépôt de la couche fonctionnelle sur au moins une partie du support, Step of depositing the functional layer on at least a part of the support,
• Etape de passivation de la surface par application d'une solution de passivation, préférentiellement aqueuse, comprenant des anions thiosulfates, Step of passivation of the surface by application of a passivation solution, preferably aqueous, comprising thiosulphate anions,
• Eventuellement suivie par une étape de rinçage par un solvant polaire protique, préférentiellement un solvant à base d'eau. • optionally followed by a rinsing step with a protic polar solvent, preferably a water-based solvent.
L' étape de dépôt de la couche fonctionnelle est réalisée par pulvérisation cathodique, éventuellement assistée d'un champ magnétique. Préférentiellement, le procédé de dépôt est réalisé sous vide. Les termes « sous vide » dé si gnent une pre s sion inférieure ou ég ale à 1 , 2 P a . P lus préférentiellement, le procédé sous vide est une technique de pulvérisation cathodique assistée d'un champ magnétique.
La solution de passivation comprenant des anions thiosulfates utilisée lors de l'étape de passivation est de préférence une solution à base d'un solvant polaire protique, le solvant préféré étant l'eau, plus préférentiellement l'eau désionisée. L'eau permet d'une part d'obtenir des concentrations en thiosulfate plus élevées et d'autre part d'éviter une contamination de la surface par du carbone. La solution de passivation est une solution comprenant une concentration en anion thiosulfate au moins supérieure ou égale à 0,1 M, de préférence au moins supérieure ou égale à 0,5 M, plus préférentiellement au moins supérieure ou égale à 0,8 M, le plus préférentiellement de l'ordre de 1,0 M. Préférentiellement, la solution de passivation est à base d'anions thiosulfate. Sous le vocable « à base de », on entend désigner que les anions thiosulfates représentent au moins 50% de la concentration des anions présents dans la solution de passivation. Les sels de thiosulfate utilisés pour la préparation de la solution de passivation sont des thiosulfates de K et/ou de Na. De préférence, la solution de passivation est une solution ne contenant que des anions thiosulfates, les autres anions susceptibles d'être présents ne l'étant que sous forme de trace. De préférence la solution de passivation est une solution aqueuse à 1,0 M en thiosulfate de Na. L'application de la solution de passivation peut être effectuée par les techniques d'application en rouleau, spray, rideau ou immersion. Dans le cas d'une application par immersion, on entend une immersion du substrat recouvert de l'empilage de couches dans la solution de passivation. La solution de passivation peut être agitée lors de l'immersion, l'agitation étant une agitation mécanique ou ultrasonique, préférentiellement l'agitation est ultrasonique pour des raisons d'uniformisation du flux de solvant vers la surface de la couche fonctionnelle à passiver. De manière préférée, la solution n'est pas agitée, l'absence d'agitation permettant un meilleur contrôle de la passivation. Préférentiellement, la solution de passivation est appliquée sur la surface à traiter à température ambiante, la durée d'application de la solution étant fonction de la concentration de ladite solution, les inventeurs ont observés que de manière surprenante l'action de la solution de passivation est optimum lorsque la durée d'application et la concentration de la solution de thiosulfate est au moins égale à t
= 4e~°'139c - 0,25 et au plus égale à t = 4e~°'139c + 0,25, préférentiellement au moins égale à t = 4e~°'139c - 0,20 et au plus égale à t = 4e~°'139c + 0,20, plus préférentiellement au moins égale à t = 4e"°'139c - 0,15 et au plus égale à t = 4e~ o,i39c + Q 2? \ç p[us préférentiellement au moins égale à t = 4e"°'139c - 0,10 et au plus égale à t = 4e"°'139c + 0,10. En modifiant la température de la solution de passivation, l'homme de métier peut aisément : The deposition step of the functional layer is carried out by cathodic sputtering, possibly assisted by a magnetic field. Preferably, the deposition process is carried out under vacuum. The terms "under vacuum" denote a pressure less than or equal to 1, 2 P a. More preferably, the vacuum process is a magnetic field assisted sputtering technique. The passivation solution comprising thiosulfate anions used during the passivation step is preferably a solution based on a protic polar solvent, the preferred solvent being water, more preferably deionized water. Water makes it possible to obtain higher thiosulphate concentrations on the one hand and to avoid carbon contamination of the surface on the other hand. The passivation solution is a solution comprising a concentration of thiosulphate anion at least greater than or equal to 0.1 M, preferably at least greater than or equal to 0.5 M, more preferably at least greater than or equal to 0.8 M, most preferably of the order of 1.0 M. Preferably, the passivation solution is based on thiosulfate anions. The term "based on" is intended to mean that the thiosulphate anions represent at least 50% of the concentration of the anions present in the passivation solution. The thiosulphate salts used for the preparation of the passivation solution are K and / or Na thiosulphates. Preferably, the passivation solution is a solution containing only thiosulphate anions, the other anions likely to be present being only in trace form. Preferably the passivation solution is a 1.0 M aqueous solution of Na thiosulfate. The application of the passivation solution can be carried out by application techniques in roll, spray, curtain or immersion. In the case of an immersion application, it is meant an immersion of the substrate covered with the stack of layers in the passivation solution. The passivation solution may be stirred during immersion, the stirring being mechanical or ultrasonic agitation, preferably the stirring is ultrasonic for reasons of uniformization of the solvent flow to the surface of the functional layer to be passivated. Preferably, the solution is not agitated, the absence of agitation allowing better control of the passivation. Preferably, the passivation solution is applied to the surface to be treated at room temperature, the duration of application of the solution being a function of the concentration of said solution, the inventors have observed that surprisingly the action of the passivation solution is optimum when the duration of application and the concentration of thiosulfate solution is at least equal to t = 4th ~ '' 139c - 0.25 and at most equal to t = 4th ~ '' 139c + 0.25, preferably at least equal to t = 4e ~ '' 139c - 0.20 and at most equal to t = 4 ° ~ '139c + 0.20, more preferably at least t = 4 "°' 139c - 0.15 and at most equal to t = 4 ~ o, i39c + Q 2 \ ç p [us preferably at? less than t = 4e " ° ' 139c - 0,10 and at most equal to t = 4e " °' 139c + 0,10 By modifying the temperature of the passivation solution, the person skilled in the art can easily:
• diminuer la durée d'application par augmentation de la température, • decrease the duration of application by increasing the temperature,
• obtenir un meilleur contrôle de l'étape de passivation par une diminution de la température. • get better control of the passivation step by decreasing the temperature.
Le solvant polaire protique utilisé lors de l'éventuelle étape de rinçage est préférentiellement de l'eau, plus préférentiellement de l'eau désionisée, par eau désionisée, on entend désigner une eau présentant une conductivité au plus inférieure ou égale à 1 μ8/αη. L'eau permet d'une part d'obtenir des concentrations en anions thiosulfates plus élevées et d'autre part d'éviter une contamination de la surface par du carbone. L'application de la solution de rinçage peut être effectuée par les technique d'application en rouleau, spray, rideau ou immersion. Dans le cas d'une application par immersion, on entend une immersion du substrat dans la solution de rinçage. Préférentiellement, la solution de rinçage est agitée lors de l'immersion, l'agitation étant une agitation mécanique ou ultrasonique. Préférentiellement l'agitation est ultrasonique, les inventeurs ayant déterminé que de manière surprenante le rinçage par ultrason contribue également à une uniformisation de la surface de la couche fonctionnelle. The protic polar solvent used during the optional rinsing step is preferably water, more preferably deionized water, deionized water, it is meant water having a conductivity at most less than or equal to 1 μ8 / αη . Water makes it possible to obtain higher concentrations of thiosulphate anions and to avoid carbon contamination of the surface. The application of the rinsing solution can be carried out by the application techniques in roll, spray, curtain or immersion. In the case of an immersion application, it is intended to immerse the substrate in the rinsing solution. Preferably, the rinsing solution is stirred during the immersion, the stirring being mechanical or ultrasonic agitation. Preferentially, the stirring is ultrasonic, the inventors having determined that, surprisingly, the ultrasonic rinsing also contributes to a uniformization of the surface of the functional layer.
Selon une mise en œuvre alternative du mode précédent, le procédé de passivation de la surface d'un substrat muni d'une couche fonctionnelle selon l'invention est tel qu'il comprend entre les étapes de dépôts de la couche fonctionnelle et l'étape de passivation, une étape supplémentaire de gravure, ladite gravure pouvant être mécanique ou par laser. Préférentiellement, la gravure est une gravure laser. Lorsqu'elle est réalisée au laser, l'étape de gravure permet
l'obtention d'une couche fonctionnelle discontinue. Cependant, cette étape induit à la surface de la couche fonctionnelle, plus particulièrement aux bords des zones de gravure l'apparition de pics, lesdits pics pouvant entraîner une augmentation jusqu'à 200% de l'épaisseur initiale de la couche fonctionnelle. Les inventeurs ont déterminé que de manière surprenante l'étape de passivation de la surface par application d'une solution de passivation comprenant des anions thiosulfates, avantageusement suivie par une étape de rinçage par un solvant polaire protique, conduit à une diminution voire une disparition desdits pics. According to an alternative implementation of the preceding mode, the passivation method of the surface of a substrate provided with a functional layer according to the invention is such that it comprises between the deposition steps of the functional layer and the step passivation, an additional step of etching, said etching being mechanical or laser. Preferably, the etching is a laser engraving. When done by laser, the etching step allows obtaining a discontinuous functional layer. However, this step induces the appearance of peaks at the surface of the functional layer, more particularly at the edges of the etching zones, said peaks possibly causing an increase of up to 200% in the initial thickness of the functional layer. The inventors have determined that, surprisingly, the step of passivation of the surface by application of a passivation solution comprising thiosulphate anions, advantageously followed by a rinsing step with a protic polar solvent, leads to a reduction or even a disappearance of said peaks.
Un au tr e o bjet de l'invention concerne un dispositif optoélectronique comprenant un substrat selon l'invention. A third subject of the invention relates to an optoelectronic device comprising a substrate according to the invention.
5. Liste des figures 5. List of figures
D'autres caractéristiques et avantages de l'invention apparaîtront plus clairement à la lecture de la description suivante d'un mode de réalisation préférentiel, donné à titre de simple exemple illustratif et non limitatif, et des dessins annexés, parmi lesquels : Other characteristics and advantages of the invention will appear more clearly on reading the following description of a preferred embodiment, given as a simple illustrative and nonlimiting example, and the appended drawings, among which:
• la figure 1 présente une observation morphologique d'un trait de gravure laser par microscopie 3D, • Figure 1 shows a morphological observation of a laser engraving line by 3D microscopy,
• la figure 2 illustre l'effet de la morphologie résultant de la gravure laser sur un dispositif OLED à faible tension d'allumage par la présence de bords brillant (A) et présente un schéma simplifié du dispositif étudié (B), FIG. 2 illustrates the effect of morphology resulting from laser etching on a low ignition voltage OLED device by the presence of shiny edges (A) and presents a simplified diagram of the device studied (B),
• la figure 3 montre l'effet de la passivation sur la morphologie de la couche gravée, avant (3A, 3B) et après passivation (3C, 3D), la figure 4 est une mesure en C-AFM illustrant l'effet de la passivation sur la conductivité des bords de gravure,
• la figure 5 est une observation topographique par microscopie 3D d'un trait de gravure laser avant passivation, après 5 minutes d'immersion dans la solution de passivation et après 15 minutes de passivation, FIG. 3 shows the effect of passivation on the morphology of the etched layer, before (3A, 3B) and after passivation (3C, 3D), FIG. 4 is a C-AFM measurement illustrating the effect of the passivation on the conductivity of the etching edges, FIG. 5 is a topographic observation by 3D microscopy of a laser etching line before passivation, after 5 minutes of immersion in the passivation solution and after 15 minutes of passivation,
• la figure 6 est une observation topographique par microscopie 3D après passivation de 5 min, avec (B)/sans utilisation (A) d'ultrasons lors du rinçage • Figure 6 is a topographic observation by 3D microscopy after passivation of 5 min, with (B) / without use (A) of ultrasound during rinsing
• la figure 7 représente de manière schématique un exemple de substrat selon l'invention FIG. 7 schematically represents an example of a substrate according to the invention
6. Description d'un mode de réalisation de l'invention 6. Description of an embodiment of the invention
Dans l'exemple suivant, une couche fonctionnelle de conduction électrique ayant comme structure à partir du support: In the following example, a functional electrical conduction layer having as structure from the support:
Ti02 (65,0 nm)/ ZnxSnyOz (5,0 nm)/ Ag (12,5 nm)/ Ti (2,5 nm)/ ZnxSnyOz (7,0 nm)/ Nitrure de Ti (1,5 nm) a été déposée par pulvérisation cathodique sur un support verrier clair ayant une épaisseur de 1,60 mm. Les conditions de dépôt pour chacune des couches sont les suivantes : Ti0 2 (65.0 nm) / Zn x Sn y O z (5.0 nm) / Ag (12.5 nm) / Ti (2.5 nm) / Zn x Sn y O z (7.0 nm) Ti / Nitride (1.5 nm) was sputtered onto a clear glass support having a thickness of 1.60 mm. The deposit conditions for each of the layers are as follows:
• les couches à base de Ti02 sont déposées à l'aide d'une cible de titane, sous une pression de 0,5 Pa dans une atmosphère Ar/02, TiO 2 -based layers are deposited using a titanium target at a pressure of 0.5 Pa in an Ar / O 2 atmosphere.
• les couches à base de ZnxSnyOz sont déposées à l'aide d'une cible d'alliage ZnSn, sous une pression de 0,5 Pa dans une atmosphère Ar/02, les couches à base d'Ag sont déposées à l'aide d'une cible d'Ag, sous une pression de 0,5 Pa dans une atmosphère d'Ar, les couches à base de Ti sont déposées à l'aide d'une cible en Ti, sous une pression de 0,5 Pa dans une atmosphère d'Ar et peuvent être partiellement oxydées par le plasma Ar/02 suivant,
• la couche d'uniformisation de propriétés électriques de surface à base de nitrure de Ti est déposée à l'aide d'une cible en Ti, sous une pression de 0,5 Pa dans une atmosphère Ar/N2 80/20. The layers based on Zn x Sn y O z are deposited using a ZnSn alloy target, at a pressure of 0.5 Pa in an Ar / O 2 atmosphere, the Ag layers are deposited using an Ag target, at a pressure of 0.5 Pa in an Ar atmosphere, the Ti-based layers are deposited using a Ti target, under a pressure of 0.5 Pa in an Ar atmosphere and can be partially oxidized by the following Ar / O 2 plasma, The uniformity layer of Ti nitride-based electrical surface properties is deposited using a Ti target at a pressure of 0.5 Pa in an Ar / N 2 80/20 atmosphere.
Ladite couche a ensuite subit une gravure laser à l'aide d'un laser de la marque Edgewave. Les caractéristiques du laser utilisé pour la gravure sont reprises dans le tableau I. Said layer then underwent laser engraving using a laser of the Edgewave brand. The characteristics of the laser used for etching are shown in Table I.
Tableau I caractéristiques du Laser utilisé lors de la gravure Table I characteristics of the Laser used during engraving
La figure 1 montre l ' effet du faisceau laser sur la couche fonctionnelle. Sous l'action du faisceau laser, la couche fonctionnelle subit des dommages topo graphiques caractéristiques se traduisant en particulier par la formation de pics morphologiques correspondant à une augmentation jusqu'à 200% de l'épaisseur initiale de la couche. Figure 1 shows the effect of the laser beam on the functional layer. Under the action of the laser beam, the functional layer undergoes characteristic topographic damage resulting in particular by the formation of morphological peaks corresponding to an increase up to 200% of the initial thickness of the layer.
Dans le cas des dispositifs organiques électroluminescents, la présence de ces pics se traduit par l'existence de courants de fuite importants et parfois par l'observation d'une émission plus prononcée sur les bords de gravure par rapport au centre du dispositif, conduisant à une non-uniformité de la lumière inacceptable du point de vue esthétique comme le montre la Figure 2A. Les courants de fuite correspondent à des courants circulant dans le sens inverse du
courant permettant le fonctionnement du dispositif OLED. Ils sont calculés sur base des densités de courant (mA/cm2) mesurées à -5V. In the case of organic electroluminescent devices, the presence of these peaks results in the existence of large leakage currents and sometimes by the observation of a more pronounced emission on the etching edges relative to the center of the device, leading to aesthetically unacceptable light non-uniformity as shown in Figure 2A. The leakage currents correspond to currents flowing in the opposite direction of the current enabling operation of the OLED device. They are calculated on the basis of current densities (mA / cm 2 ) measured at -5V.
Le substrat obtenu est ensuite immergé dans une solution aqueuse 1M en thiosulfate de Na en absence d'agitation pendant 10 minutes à température ambiante. Les effets de réparation topographique et de passivation électrique obtenus sont tels que présentés par les figures 3 et 4. Sous l'action de la solution, une nette diminution voire la disparition complète des pics morphologiques formés sous l'action du faisceau laser (Fig. 3) est associée à l'isolation électrique des bords de gravure laser observée en c-AFM (Fig. 4). L'observation par Microscopie à force atomique conductrice (de l'anglais Çonductive Atomic Force Microscopy (C-AFM)) permet en effet de mettre en évidence la réduction du pic de conductivité local correspondant au pic morphologique. Par conséquent, les courants de fuite mesurés sur les dispositifs OLED sont signifïcativement réduits. Ils peuvent être divisés d'un facteur au moins égal àlO, voire au moins égal à 100. Les microscopies 3D ont été réalisées à l'aide d'un MicroscopeThe substrate obtained is then immersed in a 1M aqueous solution of Na thiosulphate in the absence of stirring for 10 minutes at room temperature. The topographic repair and electrical passivation effects obtained are as shown in FIGS. 3 and 4. Under the action of the solution, a clear reduction or even the complete disappearance of the morphological peaks formed under the action of the laser beam (FIG. 3) is associated with the electrical isolation of the laser etching edges observed in c-AFM (Fig. 4). Observation by Conductive Atomic Force Microscopy (C-AFM) makes it possible to demonstrate the reduction of the peak of local conductivity corresponding to the morphological peak. As a result, the leakage currents measured on the OLED devices are significantly reduced. They can be divided by a factor of at least 10, or even at least 100. The 3D microscopies were carried out using a Microscope
3D de marque Leica DCM 3D. Le grossissement utilisé pour l'ensemble des images est de 50 fois. Les échelles en abscisse et en ordonnée sont représentées sur les profils 2D correspondant aux images 3D (ordre de grandeur des profils observés : environ 100 μιη de large et 100 nm de profondeur). Le microscope est utilisé en mode confocal, c'est-à-dire que la représentation 3D de l'échantillon observé est reconstituée à partir d'un ensemble d'images réalisées à différentes profondeur dans l'échantillon. Ces sections sont obtenues en positionnant le plan focal de l'objectif à ces différentes profondeurs. 3D brand Leica DCM 3D. The magnification used for all images is 50 times. The abscissa and ordinate scales are represented on the 2D profiles corresponding to the 3D images (order of magnitude of the observed profiles: approximately 100 μιη wide and 100 nm deep). The microscope is used in confocal mode, that is, the 3D representation of the observed sample is reconstructed from a set of images made at different depths in the sample. These sections are obtained by positioning the focal plane of the lens at these different depths.
Les mesures C-AFM ont été réalisées sur un appareil de marque Veeco. L 'AFM conducteur permet de capturer simultanément l 'image topographique et l'image électrique (mesure de la conductivité) de l'échantillon observé. Les caractéristiques de l'appareil utilisé sont reprises dans le tableau II. C-AFM measurements were performed on a Veeco branded device. Conductive AFM makes it possible to simultaneously capture the topographic image and the electrical image (conductivity measurement) of the observed sample. The characteristics of the apparatus used are shown in Table II.
Tableau II : Caractéristiques de l'appareil utilisé en C-AFM
mode de balayage contact pointe conductrice Ptlr5 sur pointe Si résolution spatiale 20 nm sensibilité du module 100 fA Table II: Characteristics of the apparatus used in C-AFM Ptlr5 contact point conductive tip scanning mode Si spatial resolution 20 nm module sensitivity 100 fA
La composition chimique de la solution de passivation, sa concentration en thiosulfate ainsi que sa température sont ajustées de façon à permettre de retirer uniquement l'amas de matériaux superficiels présent au niveau des bords de gravure laser, sans pour autant affecter la surface active de la couche fonctionnelle de conduction électrique. The chemical composition of the passivation solution, its concentration of thiosulfate and its temperature are adjusted so as to remove only the pile of surface materials present at the laser etching edges, without affecting the active surface of the functional layer of electrical conduction.
Le temps d'exposition doit être ajusté de façon à permettre l'élimination des pics morphologiques formés sous l'action du faisceau laser sans pour autant créer de nouveaux dommages topo graphiques. En effet, des temps d'exposition prolongés peuvent conduire à la formation de pics morphologiques secondaires comme le montre la figure 5. La figure 5 illustre l'observation topographique d'un trait de gravure laser par microscopie 3D avant immersion dans la solution de passivation, après 5 minutes et après 15 minutes d'immersion. On note l'apparition de pics secondaires après 15 minutes d'immersion. Le tableau IV présente de manière succincte l'effet de la concentration de la solution de passivation en fonction du temps de traitement, ledit traitement étant effectué à température ambiante (~25°C) :
The exposure time must be adjusted to allow the elimination of the morphological peaks formed under the action of the laser beam without creating new graphic topographic damage. Indeed, prolonged exposure times can lead to the formation of secondary morphological peaks as shown in Figure 5. Figure 5 illustrates the topographic observation of a laser engraving line by 3D microscopy before immersion in the passivation solution after 5 minutes and after 15 minutes of immersion. The appearance of secondary peaks after 15 minutes of immersion is noted. Table IV briefly shows the effect of the concentration of the passivation solution as a function of the treatment time, said treatment being carried out at room temperature (~ 25 ° C.):
Tableau III : Effet du temps de traitement de passivation en fonction de la concentration de la solution de passivation Table III: Effect of passivation treatment time as a function of the concentration of the passivation solution
Avec — , -, =, +, ++ représentant respectivement un effet de réparation topographique très négatif, négatif, sans effet, positif, très positif. Le caractère positif de la réparation se traduisant par une diminution, voire la disparition des pics liés à la gravure laser, l'effet négatif résultant de l'apparition de pics secondaires. With -, -, =, +, ++ respectively representing a very negative, negative, no effect, positive, very positive topographic repair effect. The positive nature of the repair resulting in a decrease or even the disappearance of the peaks related to laser engraving, the negative effect resulting from the appearance of secondary peaks.
L' influence de la température n'a pas été testée, mais il est bien connu par l'homme de métier que les cinétiques de dissolution sont améliorées par l'élévation de la température. The influence of temperature has not been tested, but it is well known to those skilled in the art that the kinetics of dissolution are improved by raising the temperature.
L'utilisation d'ultrasons lors de la passivation ou du rinçage, préférentiellement lors du rinçage, contribue à l'amélioration des propriétés topographiques des bords de gravure laser, ainsi qu'à l'élimination des résidus éventuels de la réaction chimique, comme illustré par la Figure 6. La figure est une observation en microscopie 3D d'un substrat selon l'invention après une passivation de 5 min dans une solution en thiosulfate de sodium, avec (B)/sans utilisation (A) d'ultrasons lors du rinçage dans de l'eau déionisée par microscopie 3D.
La figure 7 représente un exemple de substrat (1), ledit substrat comprenant un support 10 et une couche fonctionnelle (1 1 ), ladite couche fonctionnelle comprenant successivement à partir du support (10) : The use of ultrasound during passivation or rinsing, preferably during rinsing, contributes to the improvement of the topographic properties of laser etching edges, as well as the elimination of possible residues of the chemical reaction, as illustrated. 6 is a 3D microscopic observation of a substrate according to the invention after a passivation of 5 min in a solution of sodium thiosulphate, with (B) / without use (A) of ultrasound during the rinsing in deionized water by 3D microscopy. FIG. 7 represents an example of a substrate (1), said substrate comprising a support 10 and a functional layer (1 1), said functional layer comprising successively from the support (10):
• une couche barrière (110) • a barrier layer (110)
• une couche d'optimisation optique (111) An optical optimization layer (111)
• une couche de cristallisation (112) A crystallization layer (112)
• une couche sacrificielle (113) A sacrificial layer (113)
• une couche métallique à base d'argent (114) • a metal layer made of silver (114)
• une couche sacrificielle (115) A sacrificial layer (115)
• une couche d'insertion (116) une couche d'uniformisation des propriétés électriques de surface (117) ledit substrat étant soumis au traitement de passivation. An insertion layer (116), a uniformity layer of the surface electrical properties (117), said substrate being subjected to the passivation treatment.
Des exemples de substrats comportant un support en verre et une couche fonctionnelle de type bas émissif pouvant être soumise audit traitement de passivation sont présentés dans le tableau IV. Examples of substrates comprising a glass support and a low emissivity type functional layer that can be subjected to said passivation treatment are shown in Table IV.
Tableau IV : Exemples de substrats pouvant être passivés, ledit substrat étant constitué d'un support en verre extra-clair recouvert par l'une des couches fonctionnelles suivantes :
TABLEAU IV Table IV: Examples of substrates that can be passivated, said substrate consisting of an extra-clear glass support covered by one of the following functional layers: TABLE IV
ZS05 = oxyde mixte zinc étain obtenu par pulvérisation cathodique dans une atmosphère oxydante à partir d'une cible métallique d'un alliage de ZnSn à 52% de Zn et 48% de Sn ZS05 = zinc tin mixed oxide obtained by cathodic sputtering in an oxidizing atmosphere from a metal target of a ZnSn alloy at 52% Zn and 48% Sn
ZS09 = oxyde mixte zinc étain obtenu par pulvérisation cathodique dans une atmosphère oxydante à partir d'une cible métallique d'un alliage de ZnSn à 90% de Zn et 10% de Sn ZS09 = zinc tin mixed oxide obtained by sputtering in an oxidizing atmosphere from a metal target of a ZnSn alloy at 90% Zn and 10% Sn
TZO = oxyde mixte titane zirconium obtenu par pulvérisation cathodique dans une atmosphère oxydante à partir d'une cible métallique d'un alliage de TiZr à 50% de Ti et 50% de Zr
TZO = mixed titanium zirconium oxide obtained by cathodic sputtering in an oxidizing atmosphere from a metal target of a TiZr alloy at 50% Ti and 50% Zr
Claims
1. Substrat (1) comprenant un support (10), ledit support (10) comprenant sur au moins une de ses faces principales, une couche fonctionnelle (11) conférant des propriétés de conduction électrique, ladite couche fonctionnelle comprenant au moins une couche métallique, caractérisé en ce que ladite couche fonctionnelle comporte à son extrême surface opposée au support (10) au moins un composé soufré sous la forme de thiosulfate. 1. Substrate (1) comprising a support (10), said support (10) comprising on at least one of its main faces, a functional layer (11) conferring electrical conduction properties, said functional layer comprising at least one metal layer , characterized in that said functional layer comprises at its extreme surface opposite the support (10) at least one sulfur compound in the form of thiosulfate.
2. Substrat selon la revendication une, tel que la couche fonctionnelle (11) comprend au moins une couche métallique à base d'argent (114). The substrate of claim 1, such that the functional layer (11) comprises at least one silver-based metal layer (114).
3. Substrat selon une quelconque des revendications précédentes, tel que la couche fonctionnelle comprend au moins une couche barrière (110). Substrate according to any one of the preceding claims, such that the functional layer comprises at least one barrier layer (110).
4. Substrat selon une quelconque des revendications précédentes, tel que la couche métallique à base d'argent (114) comprend sur au moins une de ses faces au moins une couche sacrificielle (113, 115). 4. Substrate according to any one of the preceding claims, such that the silver-based metal layer (114) comprises on at least one of its faces at least one sacrificial layer (113, 115).
5. Substrat selon une quelconque des revendications précédentes, tel que la couche fonctionnelle comprend une couche d'uniformisation (117) des propriétés électriques de surface, ladite couche d'uniformisation (117) étant la couche la plus éloignée du support (10) au sein de la couche fonctionnelle (11). A substrate according to any one of the preceding claims, such that the functional layer comprises a uniformity layer (117) of surface electrical properties, said uniformity layer (117) being the layer furthest from the support (10) at the within the functional layer (11).
6. Substrat selon une quelconque des revendications précédentes, tel que la couche fonctionnelle comprend au moins une couche d'optimisation optique (111) insérée entre la couche métallique à base d'argent (114) et le support (10). The substrate of any preceding claim, such that the functional layer comprises at least one optical optimization layer (111) inserted between the silver-based metal layer (114) and the support (10).
7. Substrat selon une quelconque des revendications précédentes, tel que la couche fonctionnelle (11) comprend au moins une couche supplémentaire de cristallisation (112) insérée entre le support (10) et la couche métallique à base d'argent (114). Substrate according to any one of the preceding claims, such that the functional layer (11) comprises at least one additional crystallization layer (112) inserted between the support (10) and the layer silver-based metal (114).
8. Substrat selon l ' une quelconque des revendications précédentes, tel que la couche fonctionnelle (11) comprend au moins une couche supplémentaire d'insertion (116) située entre la couche métallique à base d'argent (114) et la couche mince d'uniformisation (117). A substrate according to any one of the preceding claims, such that the functional layer (11) comprises at least one additional insertion layer (116) located between the silver-based metal layer (114) and the thin-film layer (11). standardization (117).
9. Substrat selon une quelconque des revendications précédentes, tel que la couche fonctionnelle est une couche discontinue sous forme de zones adjacentes distinctes, notamment sous forme de bandes parallèles. 9. Substrate according to any one of the preceding claims, such that the functional layer is a discontinuous layer in the form of distinct adjacent zones, in particular in the form of parallel strips.
10. Procédé d'uniformisation de la surface d'un substrat muni d'une couche fonctionnelle selon une quelconque des revendications précédentes tel qu'il comprend les étapes successives suivantes : 10. A method of uniformizing the surface of a substrate provided with a functional layer according to any one of the preceding claims, such that it comprises the following successive steps:
• Etape de dépôt de la couche fonctionnelle, • Deposition step of the functional layer,
• Etape de gravure de la couche fonctionnelle, Step of etching the functional layer,
• Etape d'uniformisation de la surface par application d'une solution aqueuse comprenant des anions thiosulfates, éventuellement suivie par une étape de rinçage par un solvant à base d'eau. Step of uniformizing the surface by application of an aqueous solution comprising thiosulphate anions, optionally followed by a rinsing step with a water-based solvent.
11. Procédé d'uniformisation de la surface d'un substrat muni d'une couche fonctionnelle selon la revendication précédente, tel que la gravure est une gravure laser. 11. A method of uniformizing the surface of a substrate provided with a functional layer according to the preceding claim, such that the etching is a laser etching.
12. Procédé selon une quelconque des revendications 10 à 11, tel que l'étape d'uniformisation est effectuée sous agitation. 12. Method according to any one of claims 10 to 11, such that the uniformization step is carried out with stirring.
13. Procédé selon une quelconque des revendications 10 à 12, tel que la solution de passivation est une solution comprenant une concentration en anion thiosulfate au moins supérieure ou égale à 0,1 M. 13. Process according to any one of claims 10 to 12, such that the passivation solution is a solution comprising a thiosulphate anion concentration of at least greater than or equal to 0.1 M.
14. Procédé selon une quelconque des revendication 10 à 13, tel que la durée d'application (t en min.) et la concentration de la solution de thiosulfate (c en M) est au moins égale à t = 4e"°'139c - 0,25 et au plus égale à t = 4e-°'139c + 0,25. 14. Process according to any one of Claims 10 to 13, such that the duration of application (t in min.) And the concentration of the thiosulphate solution (c in M) is at least equal to t = 4e " ° ' 139c 0.25 and at most equal to t = 4.degree. 139c + 0.25.
15. Dispositif optoélectronique comprenant un substrat selon une quelconque des revendications 1 à 9. An optoelectronic device comprising a substrate according to any one of claims 1 to 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE201100681 | 2011-11-23 | ||
| PCT/EP2012/069927 WO2013075879A1 (en) | 2011-11-23 | 2012-10-09 | Substrate with a functional layer comprising a sulphurous compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2783402A1 true EP2783402A1 (en) | 2014-10-01 |
Family
ID=47045009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12774994.3A Withdrawn EP2783402A1 (en) | 2011-11-23 | 2012-10-09 | Substrate with a functional layer comprising a sulphurous compound |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US9293707B2 (en) |
| EP (1) | EP2783402A1 (en) |
| WO (1) | WO2013075879A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10179946B2 (en) * | 2017-03-03 | 2019-01-15 | Guardian Glass, LLC | Coated article having low-E coating with IR reflecting layer(s) and niobium bismuth based high index layer and method of making same |
| GB201916515D0 (en) * | 2019-11-13 | 2019-12-25 | Pilkington Group Ltd | Coated glass substrate |
| FR3107703B1 (en) * | 2020-02-28 | 2023-06-23 | Saint Gobain | SOLAR CONTROL GLAZING INCLUDING A LAYER OF TITANIUM NITRIDE |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2913146B1 (en) * | 2007-02-23 | 2009-05-01 | Saint Gobain | DISCONTINUOUS ELECTRODE, ORGANIC ELECTROLUMINESCENCE DEVICE INCORPORATING THE SAME, AND THEIR MANUFACTURING |
| JP2009026786A (en) * | 2007-07-17 | 2009-02-05 | Chisso Corp | Cleaning liquid and cleaning method for semiconductor device having gold electrode or gold wiring |
-
2012
- 2012-10-09 EP EP12774994.3A patent/EP2783402A1/en not_active Withdrawn
- 2012-10-09 WO PCT/EP2012/069927 patent/WO2013075879A1/en active Application Filing
- 2012-10-09 US US14/360,462 patent/US9293707B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
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| See references of WO2013075879A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US9293707B2 (en) | 2016-03-22 |
| WO2013075879A1 (en) | 2013-05-30 |
| US20140319687A1 (en) | 2014-10-30 |
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