EP1532225A1 - Etching pastes for titanium oxide surfaces - Google Patents
Etching pastes for titanium oxide surfacesInfo
- Publication number
- EP1532225A1 EP1532225A1 EP03790830A EP03790830A EP1532225A1 EP 1532225 A1 EP1532225 A1 EP 1532225A1 EP 03790830 A EP03790830 A EP 03790830A EP 03790830 A EP03790830 A EP 03790830A EP 1532225 A1 EP1532225 A1 EP 1532225A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- etching
- acid
- crystalline
- amorphous
- total amount
- 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- Withdrawn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
- 238000005530 etching Methods 0.000 title claims abstract description 130
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims description 39
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 239000002562 thickening agent Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002318 adhesion promoter Substances 0.000 claims description 5
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- 239000013008 thixotropic agent Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229960005215 dichloroacetic acid Drugs 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 238000007788 roughening Methods 0.000 claims description 3
- 239000011877 solvent mixture Substances 0.000 claims description 3
- 230000009974 thixotropic effect Effects 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- -1 titanium halides Chemical class 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000003667 anti-reflective effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 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
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QBNKFXYJSJOGEL-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ti+4] QBNKFXYJSJOGEL-UHFFFAOYSA-N 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000003631 wet chemical etching Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
Definitions
- the present invention relates to new etching media in the form of printable and dispensable etching pastes for etching titanium oxide surfaces of the general composition Ti x O y , and the use of these etching pastes.
- glasses are understood to mean materials containing titanium and oxygen which are present in the solid amorphous state without crystallization and which have a high degree of disorder in the microstructure due to the lack of long-range order.
- Layers of such amorphous materials can be produced, for example, by hydrolysis of titanium halides such as TiCl 4 , hydrolysis or pyrolysis of organic titanium precursors such as tetraisopropyl orthotitanate in an APCVD process [1], the low-pressure or plasma-assisted CVD process (LP or PE-CVD) [2].
- APCVD process APCVD
- LP or PE-CVD plasma-assisted CVD process
- Crystalline compounds are the Ti0 2 modifications rutile, anatase and brookite, the TiO modification isotype of the rock salt and the Ti 2 0 3 crystallizing in a corundum lattice structure.
- the invention relates both to the etching of titanium and oxygen-containing crystalline, partially crystalline or amorphous surfaces Ti x O y uniform solid non-porous and porous solids, and to the etching of surfaces of non-porous and porous Ti x O y layers of variable thickness on other substrates (eg ceramics, metal sheets, silicon wafers) by various methods known to the person skilled in the art (for example, CVD, PVD, spray / spin-on / off of Ti-O containing precursors) dire g, were.
- Highly efficient crystalline silicon solar cells with efficiencies> 16% usually have a textured, passivated, anti-reflective front with a two-stage emitter and a passivated back with reflective rear contacts and local back surface field (BSF).
- BSF back surface field
- any structure can be selectively etched in surfaces and layers directly by laser-assisted etching processes [3] or after masking has been carried out wet-chemically [4, 5] or by dry etching processes [6].
- the laser beam scans the entire etching pattern point by point on the surface, which in addition to a high degree of precision also requires considerable adjustment and time.
- optical microlenses arranged in arrays are used to split the laser beam and to produce a row of punctiform openings in the antireflection layer designed in accordance with the array [7].
- the wet chemical and dry etching processes involve material inks. ve, time and costly process steps:
- Photolithography production of a negative or positive of the etching structure (depending on the lacquer), lacquering of the substrate surface (e.g. by spin coating with a liquid photoresist), drying of the photoresist, exposure of the lacquered substrate surface, development, rinsing, drying if necessary
- Immersion process eg wet etching in wet chemical banks: immersing the substrates in the etching bath, etching process, multiple rinsing in H 2 0
- etching solution is applied to a rotating substrate or sprayed onto a substrate, etching process without / with energy input (e.g. photo etching, rinsing, drying)
- Dry etching processes such as Plasma etching in expensive vacuum systems or etching with reactive gases in flow reactors
- etching pastes have proven successful in solar technology for etching silicon nitride or silicon dioxide layers.
- the pastes used are pressure-capable and dispensable, homogeneous particle-free etching pastes with non-Newtonian flow behavior.
- these pastes have not proven to be optimal for the etching of titanium oxide layers in terms of etching rate, selectivity and edge sharpness.
- the object of the present invention is also to provide a simple method for etching titanium oxide layers.
- a printable and dispensable etching medium in the form of an etching paste with non-Newtonian; preferably thixotropic flow behavior for the etching of amorphous, crystalline or partially crystalline surfaces from titanium oxides, which is effective at 15-50 ° C.
- the present invention therefore also relates to an etching medium which contains ammonium hydrogen difluoride as an etching component for oxidic surfaces, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene carbonate and water as a solvent, formic acid as an organic acid and polyvinylpyrolidone as a thickening agent.
- Amorphous, crystalline or semi-crystalline surfaces made of titanium oxides can be etched according to the invention in a process which is simple to carry out, in that such an etching medium is applied to a surface to be etched and is removed again after an exposure time of 0.1-15 min.
- the etching medium can be applied over the whole area or, according to the etching structure template, only at the locations where an etching is desired and, after the etching has been carried out, rinsed with a solvent or solvent mixture or burned in the oven.
- the etching media can be applied to the surfaces to be etched using screen, stencil, tampon, stamp, ink-jet and manual printing processes and dispenser technology.
- the etching media according to the invention can be used to produce markings and markings and to improve the adhesion of Ti x O y glasses, ceramics and other Ti x O y-based systems with other materials by roughening.
- the etching media according to the invention can advantageously be used for etching amorphous, partially crystalline and crystalline Ti x O y systems in the form of uniform solid non-porous and porous solids or corresponding non-porous and porous layers of variable thickness which have been produced on other substrates.
- the etching pastes according to the invention can be used with particularly good results in the production process of solar cells for removing amorphous, partially crystalline and crystalline Ti x O y layers, for selectively opening anti-reflective layers from Ti x O y systems for producing two-stage selective emitters and / or locally Use p + back surface fields.
- the present invention thus also relates to amorphous, partially crystalline or crystalline surfaces made of titanium oxides which have been treated with the etching media according to the invention having the composition mentioned above.
- the invention relates to printable and dispensable etching pastes which are suitable for etching titanium oxide surfaces, the general formula Ti x O y and their layers of variable thickness, and their use in a - in comparison to the usual wet and dry etching processes - inexpensive, continuous, suitable for high throughputs, as well as technologically simple, printing, dispensing / etching processes.
- the printable and dispensable etching pastes described according to the invention are - compared to liquid etching agents for Ti x O y -based systems such as inorganic mineral acids (hydrofluoric acid, hot concentrated sulfuric acid) and alkaline / basic etching agents (molten alkali metal). droxides and carbonates) - much easier, safer and easier to handle.
- liquid etching agents for Ti x O y -based systems such as inorganic mineral acids (hydrofluoric acid, hot concentrated sulfuric acid) and alkaline / basic etching agents (molten alkali metal). droxides and carbonates) - much easier, safer and easier to handle.
- a technique with a high degree of automation and throughput that is suitable for the transfer of the etching paste to the area to be etched is the printing and dispensing technique.
- the screen, stencil, tampon, stamp, ink-jet printing processes are printing processes known to the person skilled in the art.
- etching structure template Depending on the sieve, template, cliché, stamp design or cartridge and dispenser control, it is possible to selectively apply the printable and dispensable etching pastes described in accordance with the invention according to the etching structure template only at those locations where etching is desired or can also be applied over the entire surface. All masking and lithography steps as described under A) are eliminated by the selective application.
- the etching process takes place with or without additional energy input, e.g. in the form of heat radiation (with IR lamp, up to approx. 300 ° C lamp temperature) instead.
- the printable and dispensable etching pastes are rinsed off from the etched surface with a suitable solvent or burned out.
- the etching depth in Ti x O y -based systems and their layers of variable thickness can be adjusted by varying the following sizes and, in the case of selective structure etching, the edge sharpness of the etching structures can also be set:
- Additives such as defoamers, thixotropic agents, leveling agents, deaerators, adhesion promoters
- the etching time can be between a few seconds and several minutes.
- the printable and dispensable etching pastes are composed of:
- additives such as Defoamers, thixotropic agents, leveling agents, deaerators, adhesion promoters
- etching effect of the printable and dispensable etching pastes described according to the invention on surfaces of Ti x O y -based systems is based on the use of solutions of ammonium hydrogen difluoride with or without the addition of acid. These etching pastes are already at room temperature or become effective through additional energy input (eg heat radiation from an IR lamp, up to approx. 300 ° C lamp temperature).
- the proportion of the etching component used is in a concentration range of 8.5-9.5% by weight based on the total amount of the etching paste.
- Suitable inorganic and / or organic solvents and / or mixtures of these can be:
- ethers such as ethylene glycol monobutyl ether, triethylene glycol monomethyl ether
- carbonic acid esters such as propylene carbonate
- organic acids such as formic acid, acetic acid, lactic acid or similar
- the proportion of solvents is in the range of 52-57% by weight based on the total amount of the etching paste.
- the viscosity of the printable and dispensable etching pastes described according to the invention is achieved by network-forming thickeners which swell in the liquid phase and can be varied depending on the desired field of use.
- the printable and dispensable etching pastes described according to the invention include all etching pastes that do not have a constant viscosity of the shear rate, in particular etching pastes with a shear-thinning effect.
- the network created by thickeners breaks down under shear stress. The network can be restored without a time delay (structurally viscous etching pastes with plastic or pseudoplastic flow behavior) or with a time delay (etching pastes with thixotropic flow behavior).
- the thickeners polyvinyl pyrolidone (PVP) or various celluloses can be used individually and / or in combinations with one another.
- the proportion of the thickeners which is required for the targeted adjustment of the viscosity range and in principle for the formation of a printable and dispensable paste is in the range from 10.5 to 11.5% by weight, based on the total amount of the etching paste.
- Organic and inorganic acids whose pK a value between 0 - 5. li. gene, can be added to the printable and dispensable etching pastes described according to the invention.
- Inorganic mineral acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid as well as organic acids, especially formic acid, improve the etching effect of the printable and dispensable etching pastes.
- acid is added, the proportion of acid / s is 24-26% by weight, based on the total amount of the etching paste.
- Additives with properties that are advantageous for the desired purpose are defoamers (e.g. TEGO® Foamex N), thixotropic agents (e.g. BYK® 410, Borchigel® Thixo2), leveling agents (e.g. TEGO® Glide ZG 400), deaerators (e.g. TEGO® Airex 985) and adhesion promoters (e.g. Bayowet® FT 929). These can have a positive effect on the printability of the etching paste.
- the proportion of additives is in the range of 0-0.5% by weight based on the total amount of the etching paste.
- Areas of application for the etching pastes according to the invention can be found in the solar cell industry, in particular in the production of photovoltaic components such as solar cells or photodiodes.
- etching pastes which are printable and dispensable according to the invention can in particular be used wherever a full-area and / or structured etching of surfaces of Ti x O y -based systems is desired.
- etching pastes which can be printed according to the invention can be used in particular wherever a full-area and / or structured etching of Ti x O y layers is desired.
- the screen, stencil, tampon, ink-jet printing processes and dispenser technology are suitable techniques for applying the etching pastes in the desired manner.
- a manual order is also possible.
- the solvent mixture and acid are placed in a PE beaker.
- the NH 4 HF 2 solution is then added.
- the thickener is added successively with stirring (approx. 900 rpm). Filling into containers takes place after a short standstill. This service life is necessary so that the bubbles formed in the etching paste can dissolve.
- the etching rates determined on a Ti x O y layer produced with APCVD depend on the salt and acid concentration and are between 20-150 nm / min in the case of a linear application. For example, with a selective application (line width of 250 ⁇ m) of Example 1 at room temperature 70 nm / min, at 50 ° C etching temperature 140 nm / min.
- the etching paste obtained is stable in storage, easy to handle and printable. It can e.g. with water from the printed material or from the paste carrier (sieve, squeegee, stencil, stamp, cliché, cartridge, dispenser etc.) or burned out in the oven.
- the paste carrier sieve, squeegee, stencil, stamp, cliché, cartridge, dispenser etc.
- Example 2 The following etching pastes can be produced analogously to the etching paste described in Example 1: Example 2
- Example 4 24 g triethylene glycol monomethyl ether 50 g 20% NH 4 HF 2 solution 8 g formic acid 1.5 g tylose 4000 (hydroxyethyl cellulose)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10239656A DE10239656A1 (en) | 2002-08-26 | 2002-08-26 | Etching pastes for titanium oxide surfaces |
DE10239656 | 2002-08-26 | ||
PCT/EP2003/008395 WO2004020551A1 (en) | 2002-08-26 | 2003-07-30 | Etching pastes for titanium oxide surfaces |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1532225A1 true EP1532225A1 (en) | 2005-05-25 |
Family
ID=31502076
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03790830A Withdrawn EP1532225A1 (en) | 2002-08-26 | 2003-07-30 | Etching pastes for titanium oxide surfaces |
Country Status (9)
Country | Link |
---|---|
US (1) | US20060118759A1 (en) |
EP (1) | EP1532225A1 (en) |
JP (1) | JP2005536614A (en) |
KR (1) | KR20050058410A (en) |
CN (1) | CN1678714A (en) |
AU (1) | AU2003255325A1 (en) |
DE (1) | DE10239656A1 (en) |
TW (1) | TW200407463A (en) |
WO (1) | WO2004020551A1 (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030148024A1 (en) * | 2001-10-05 | 2003-08-07 | Kodas Toivo T. | Low viscosity precursor compositons and methods for the depositon of conductive electronic features |
US6951666B2 (en) * | 2001-10-05 | 2005-10-04 | Cabot Corporation | Precursor compositions for the deposition of electrically conductive features |
US20030108664A1 (en) * | 2001-10-05 | 2003-06-12 | Kodas Toivo T. | Methods and compositions for the formation of recessed electrical features on a substrate |
WO2003035279A1 (en) * | 2001-10-19 | 2003-05-01 | Superior Micropowders Llc | Tape compositions for the deposition of electronic features |
EP2032291A2 (en) * | 2006-06-19 | 2009-03-11 | Cabot Corporation | Metal-containing nanoparticles, their synthesis and use |
DE102006051735A1 (en) * | 2006-10-30 | 2008-05-08 | Merck Patent Gmbh | Printable medium for the etching of oxidic, transparent, conductive layers |
US8017505B2 (en) * | 2006-11-30 | 2011-09-13 | Seiko Epson Corporation | Method for manufacturing a semiconductor device |
ES2556127T3 (en) * | 2007-08-31 | 2016-01-13 | The Procter & Gamble Company | Liquid acid hard surface cleaning composition |
JP5575771B2 (en) * | 2008-09-01 | 2014-08-20 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Edge removal of thin-layer solar modules by etching |
CN101768445B (en) * | 2010-01-29 | 2014-02-19 | 东莞市亚马电子有限公司 | Environment-friendly sull etching paste |
JP2013534944A (en) | 2010-06-14 | 2013-09-09 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Cross-linked and multi-phase etching pastes for high resolution feature patterning |
WO2012083082A1 (en) | 2010-12-15 | 2012-06-21 | Sun Chemical Corporation | Printable etchant compositions for etching silver nanoware-based transparent, conductive film |
CN102363885B (en) * | 2011-10-12 | 2013-08-21 | 常州大学 | Pretreatment solution for selective stripping of silver coating and quantitative analysis of elements in silver coating |
WO2013169884A1 (en) * | 2012-05-10 | 2013-11-14 | Corning Incorporated | Glass etching media and methods |
CN107814491A (en) * | 2017-12-14 | 2018-03-20 | 天津美泰真空技术有限公司 | A kind of flat glass substrate etching solution |
CN108585530A (en) * | 2018-04-20 | 2018-09-28 | 广东红日星实业有限公司 | A kind of glass etching liquid and preparation method thereof |
CN112430815B (en) * | 2020-11-23 | 2023-06-30 | 南通卓力达金属科技有限公司 | Etching solution and preparation method and application thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3326803A (en) * | 1964-04-27 | 1967-06-20 | Wyandotte Chemicals Corp | Aluminum brightener composition |
DD153360A1 (en) * | 1980-10-01 | 1982-01-06 | Heinz Schicht | MATTRESS PASTE FOR GLASS |
US4759823A (en) * | 1987-06-02 | 1988-07-26 | Krysalis Corporation | Method for patterning PLZT thin films |
JP3337622B2 (en) * | 1997-07-16 | 2002-10-21 | 松下電器産業株式会社 | Selective etchant and method of manufacturing semiconductor device using the etchant |
US6670281B2 (en) * | 1998-12-30 | 2003-12-30 | Honeywell International Inc. | HF etching and oxide scale removal |
US6287890B1 (en) * | 1999-10-18 | 2001-09-11 | Thin Film Module, Inc. | Low cost decal material used for packaging |
AU2001242510B2 (en) * | 2000-04-28 | 2006-02-23 | Merck Patent Gmbh | Etching pastes for inorganic surfaces |
DE10101926A1 (en) * | 2000-04-28 | 2001-10-31 | Merck Patent Gmbh | Etching pastes for inorganic surfaces |
CN1218222C (en) * | 2000-07-10 | 2005-09-07 | Ekc技术公司 | Compsns. for cleaning organic and plasma etched residues for semiconductor devices |
-
2002
- 2002-08-26 DE DE10239656A patent/DE10239656A1/en not_active Withdrawn
-
2003
- 2003-07-30 US US10/524,847 patent/US20060118759A1/en not_active Abandoned
- 2003-07-30 WO PCT/EP2003/008395 patent/WO2004020551A1/en not_active Application Discontinuation
- 2003-07-30 EP EP03790830A patent/EP1532225A1/en not_active Withdrawn
- 2003-07-30 AU AU2003255325A patent/AU2003255325A1/en not_active Abandoned
- 2003-07-30 JP JP2004531831A patent/JP2005536614A/en active Pending
- 2003-07-30 CN CNA038200813A patent/CN1678714A/en active Pending
- 2003-07-30 KR KR1020057002920A patent/KR20050058410A/en not_active Application Discontinuation
- 2003-08-22 TW TW092123222A patent/TW200407463A/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO2004020551A1 * |
Also Published As
Publication number | Publication date |
---|---|
KR20050058410A (en) | 2005-06-16 |
US20060118759A1 (en) | 2006-06-08 |
TW200407463A (en) | 2004-05-16 |
CN1678714A (en) | 2005-10-05 |
AU2003255325A1 (en) | 2004-03-19 |
WO2004020551A1 (en) | 2004-03-11 |
DE10239656A1 (en) | 2004-03-11 |
JP2005536614A (en) | 2005-12-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1276701B1 (en) | Etching pastes for inorganic surfaces | |
EP1532225A1 (en) | Etching pastes for titanium oxide surfaces | |
EP1535318B1 (en) | Etching pastes for silicon surfaces and layers | |
EP1240673B1 (en) | Method for raw etching silicon solar cells | |
EP0914486B1 (en) | Coating substrate | |
EP1435116B1 (en) | Combined etching and doping substances | |
EP2345091B1 (en) | Edge deletion of thin-layer solar modules by means of etching | |
DE102006051952A1 (en) | Particle-containing etching pastes for silicon surfaces and layers | |
EP2683777A2 (en) | Metallisation barrier based on aluminium oxide | |
DE102005033724A1 (en) | Printable etching media for silicon dioxide and silicon nitride layers | |
DE102006051735A1 (en) | Printable medium for the etching of oxidic, transparent, conductive layers | |
WO2006074791A1 (en) | Printable medium for the etching of silicon dioxide and silicon nitride layers | |
WO2011050889A2 (en) | Method for producing solar cells having a selective emitter | |
DE102005035255A1 (en) | Etching media for oxide, transparent, conductive layers | |
WO2016107661A1 (en) | Laser doping of semiconductors | |
EP2938763A1 (en) | Printable diffusion barriers for silicon wafers | |
EP3513439A1 (en) | Method for producing electrical contacts on a component | |
WO2016165812A1 (en) | Screen-printable boron doping paste with simultaneous inhibition of phosphorus diffusion in co-diffusion processes | |
CN110699729B (en) | Rare earth tetrafluoride NalnF4Film and preparation method thereof | |
DE102009007136A1 (en) | Etching mixture for producing a structured surface on silicon substrates | |
DE10101926A1 (en) | Etching pastes for inorganic surfaces | |
CN110699728B (en) | Rare earth trifluoride LnF3Film and preparation method thereof | |
WO2016150548A2 (en) | Printable, pasty diffusion and alloy barrier for producing high-efficient crystalline silicon solar cells | |
EP3366639A1 (en) | Method for producing structured coatings | |
WO2011161038A1 (en) | Method for increasing the translucency of a substrate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20050108 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
DAX | Request for extension of the european patent (deleted) | ||
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: STOCKUM, WERNER Inventor name: KUEBELBECK, ARMIN Inventor name: KLEIN, SYLKE |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20080201 |