WO2015142295A1 - Method for synthesis of tetragonal zirconia thin films suitable for catalytic devices - Google Patents
Method for synthesis of tetragonal zirconia thin films suitable for catalytic devices Download PDFInfo
- Publication number
- WO2015142295A1 WO2015142295A1 PCT/SI2015/000012 SI2015000012W WO2015142295A1 WO 2015142295 A1 WO2015142295 A1 WO 2015142295A1 SI 2015000012 W SI2015000012 W SI 2015000012W WO 2015142295 A1 WO2015142295 A1 WO 2015142295A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zirconium
- thin film
- zirconium oxide
- tetragonal
- oxygen
- Prior art date
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000010409 thin film Substances 0.000 title claims abstract description 51
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 230000003197 catalytic effect Effects 0.000 title description 19
- 230000015572 biosynthetic process Effects 0.000 title description 12
- 238000003786 synthesis reaction Methods 0.000 title description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 46
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 16
- 238000011282 treatment Methods 0.000 claims abstract description 15
- 231100001261 hazardous Toxicity 0.000 claims abstract description 7
- 239000012495 reaction gas Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 230000001699 photocatalysis Effects 0.000 claims description 41
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 36
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 36
- 239000010955 niobium Substances 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 238000009489 vacuum treatment Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000001771 vacuum deposition Methods 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 230000006378 damage Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001093 Zr alloy Inorganic materials 0.000 claims 1
- 239000003570 air Substances 0.000 claims 1
- -1 nitric oxides Chemical compound 0.000 claims 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 43
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 239000005711 Benzoic acid Substances 0.000 description 15
- 235000010233 benzoic acid Nutrition 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 230000006641 stabilisation Effects 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- 239000002019 doping agent Substances 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001341 grazing-angle X-ray diffraction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N o-dihydroxy-benzene Natural products OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000017274 Diospyros sandwicensis Nutrition 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 241000282838 Lama Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 210000001072 colon Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000011351 dental ceramic Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910002070 thin film alloy Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5826—Treatment with charged particles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
- H01J37/3402—Gas-filled discharge tubes operating with cathodic sputtering using supplementary magnetic fields
- H01J37/3405—Magnetron sputtering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
- H01J37/3411—Constructional aspects of the reactor
- H01J37/3414—Targets
- H01J37/3426—Material
- H01J37/3429—Plural materials
Definitions
- the invention relates to methods for synthesizing stable tetragonal zirconium oxide in form of thin films with pre-selected surface morphologies using a thin film alloy.
- the invention also relates to methods for treating said alloy with a reaction gas in the presence of strong magnetic fields.
- zirconia exhibits good photo-catalytic activity; thus it is found in catalytic applications [J.-M. Herrmann, Top. Catal. 34, 49 (2005); US5532198; US0039814].
- the most widely used transition metal oxides that exhibit high efficiency of photo-catalytic activity are the metastable crystal structures of the anatase Ti0 2 and the tetragonal Zr0 2 (zirconia).
- the photo-catalytic activity of a solid is determined by two physical properties; the optical band gap, which is determined as the energy gap between the valence and the conduction bands and the crystal structure of the solid.
- the influence of the optical band gap in the photo-catalysis process is because the photo-catalytic activity may occur when a semiconductor solid is irradiated by a light source composed by photons with energy above the optical band gap of the solid, such as UV irradiation by a Xenon lamp or sun irradiation. In that case electrons from the valence band are excited to the conduction band and a pair of electron-hole (exciton) is created. Consequently, the electrons and the holes, which are separated by the band gap, create a polarization potential on the surface of the solid, which, if it is sufficient enough, causes the oxidation or the reduction of several chemical substances [US0039814].
- the second physical property that determines the photo-catalytic efficiency of a catalytic solid is its crystal structure. This is because the crystal structure that is produced by specific electronic configuration has as a result the creation of different energy levels or states in the valence and conduction bands of the photo-catalytic solid, so even if two photo- catalytic solids with different crystal structures, i.e. monoclinic and tetragonal Zr0 2 , they may have the similar values of their band gaps [Y. Gao et al., Chem. Mater. 16, 2615 (2004)], they will have different photo-catalytic efficiencies.
- a method to examine and determine the photo-catalytic activity of a solid is the photo-catalytic activity in aqueous solutions. These measurements can be performed at constant temperature in a UV transparent tube, in which the catalyst is placed. The aqueous solution consisted of the molecules to be catalyzed is leaked in the tube. Prior to UV irradiation the system is left in the dark for 30 minutes in order to reach adsorption equilibrium onto the photo-catalyst surface. Thereafter, the photo-catalyst is irradiated by UV source, i.e. Xenon lamp filtered by any IR emission to avoid any heating of the photo-catalyst.
- UV source i.e. Xenon lamp
- the initial and the catalyzed solutions are characterized by liquid chromatography for the determination of the catalytic yield of the photo-catalyst.
- the photo-catalytic activity differs for each photo-catalyst.
- the photo-catalytic studies have shown that zirconia exhibits high photo-catalytic efficiency as far as the catalysis of hazardous hydrocarbons, chlorides and nitrides is concerned (CH 4 , C 2 H 6 , HCHO, CH 3 OH, and HCOOH, CCI 4 , NO x [K.A. Bethke et al., Catal. Lett. 25, 37 (1994); C.-C. Lo et al., Sol. Energ. Mat. Sol. C. 91 , 1765 (2007); Y.-C. Chien et al., J. Hazard. Mater. 151 , 461 (2008)].
- Zirconium oxide is found in different crystalline forms such as the monoclinic and tetragonal forms, and in the form of a thin film or powder. Regardless the form the stabilization of zirconium oxide is a difficult task. The knowledge on formation of zirconium oxide in thin solid films of improved photo-catalytic activity is limited, too. An important advantage of the zirconium oxide in the form of a thin film is ability to be deposited on various technological products and components, for example the industrial pipes, parts of vehicles, roofs and windows, what allows for photo- catalytic destruction of hazardous molecules that may be presented in the atmosphere or formed in industry.
- Another important advantage of the material in the form of a thin film is ability to be cleaned rather easily, especially when it becomes polluted before application, and the cleaning procedure does not cause a decrease of the catalytic activity. Cush losses are typical for zirconium oxide in the form of dust.
- the technical problem solved by the methods of invention is the method for synthesizing stabile zirconium oxide in tetragonal form in the thin films, the material having superior photo-catalytic and being suitable for industrial production and use.
- the stabilization of the tetragonal zirconia is established by Zr0 2 growth or synthesis with aliovalent dopants, such as Y 3+ , Ca 2+ and Na + or even tetravalent Si + , Ce 4+ , Ge 4+ and pentavalent Nb 5+ , Ta 5+ dopants.
- aliovalent dopants such as Y 3+ , Ca 2+ and Na + or even tetravalent Si + , Ce 4+ , Ge 4+ and pentavalent Nb 5+ , Ta 5+ dopants.
- the root for the stabilization involves the lower valence and larger dopants (in comparison with the Zr + ions) and it is believed to occur through the replacement of Zr 4+ ions by aliovalent ions that lead to the creation of oxygen vacancies, which consequently force the solid in the formation of an eight coordinated polyhedron that is much closer to the symmetry of the tetragonal zirconia [J.C. Ray et al., J. Am. Ceram. Soc. 86, 514 (2003); J.C. Ray et al., Mater. Lett. 53, 145 (2002)] when dopants of lower valence and larger size are used (Nb, Ta, V) [G. Gopalakrishnan and S. Ramanathan, J.
- the stabilization occurs for two reasons: a) the zirconia matrix is more positively charged and so the eight coordination symmetry is promoted and also the strong bonds of the Ta-0 or the Nb-O-Zr prohibit the reorientation of the atoms to form the stable monoclinic phase of Zr0 2 at room temperature; b) stabilization of tetragonal zirconia can be established also when small size and low valence dopants are used. This is because oxygen vacancies are created and so a smaller unit cell can be promoted forming the tetragonal phase, which has smaller volume unit cell than the monoclinic zirconia [V. Ramaswamy et al., Catal. Today 97, 63 (2004)].
- Patent US20060245999 teaches a procedure for synthesis of tetragonal zirconium, the procedure involves the following steps: (a) addition of zirconium precursor to precipitation substance, (b) exposure of first precipitate in liquids to temperatures higher than 80°C but lower than 120°C for one hour, so that a molten mixture forms, (c) drying the mixture in order to obtain a dry amorphous zirconium, and (d) firing the dry amorphous zirconium to final zirconium containing about 99.9% tetragonal zirconium.
- the aliovalent dopants can be classified as donors and acceptors meaning that they act as valence substitutions or as lower valence ions, respectively, considering the ionic charge of the Zr + of zirconia [S.-Y. Chu et al., Integr. Ferroelectr. 58, 1293 (2003)]. Therefore, production of zirconia with Nb 5+ and Cu 2, + ionic charged dopants is expected to have enhanced photo-catalytic activity.
- the key feature of the invention is a method for synthesizing tetragonal zirconium oxide in the form of thin films comprising of two crucial steps.
- a glassy alloy is deposited onto a substrate by a suitable industrial-size method, the glassy alloy containing a large quantity of zirconium with addition of one or more elements selected from the group comprising copper, titanium and niobium, the selected materials serving for stabilization and improvement of the photo-catalytic properties.
- oxidation is performed using oxygen or oxygen- containing gas at the presence of strong electromagnetic fields. The method is faster and cheaper than any other known method for synthesizing tetragonal zirconium oxide in the form of thin films.
- the synthesized tetragonal zirconium oxide in the form of thin films have improved properties as compared to known photo-catalytic materials and is useful for application of photo- catalytic devices, what has been proved by measuring catalytic activity for a couple of hazardous compounds, i.e. Di-tert butyl catechol (DTBC) and benzoic acid.
- DTBC Di-tert butyl catechol
- Figure 1 Amorphous structure of ternary metallic glassy (MG) Zr 6 gCu2oNbn films prepared according to the methods of invention. (XRD)
- the aspect of this invention is a novel method for the production of photo-catalytic zirconia coatings by a two-step industrial scale process.
- a proper Zr-based metallic glassy film is grown by an industrial scale deposition technique, which in this invention was chosen to be the magnetron sputtering.
- the incorporation of Cu is crucial, due to its high glassy forming ability [A. Inoue et al., J. Non-Cryst. Solids 156-158, 473 (1993)].
- the industrial scale growth of stabilized zirconia coatings with enhanced photo-catalytic activity the incorporation of Cu in the oxidation metallic glassy film template is expected to increase the photo-catalytic efficiency of the proposed embodiment by the formation of CuO.
- ternary Zr-based metallic glassy films with additional elements can be grown by magnetron sputtering.
- Nb was chosen for two reasons; a) it is a known stabilization element of zirconia and b) considering the ion Zr 4+ it could enhance the photo-catalytic efficiency as a donor element.
- the metallic glassy films are used as templates for a fast (the order of magnitude is 10 seconds) treatment and low cost (no calcination procedures are needed) oxidation by oxygen in presence of a magnetic field.
- the Zr-based metallic glassy film template under a strong RF magnetic field is heated up to few hundred degrees of Celsius, while the atomic oxygen radicals (ATOX) oxidize the template.
- ATOX atomic oxygen radicals
- the methods of invention comprise the steps of:
- the metallic glassy and the tetragonal zirconia can be performed at the same chamber. That is easy to be constructed by placing, using an in vacuum transfer arm, the induction coil around the deposited metallic glassy Zr 6 9Cu 2 oNbn film and leaking oxygen instead of argon.
- the said high-vacuum treatment chamber is used only for deposition of said thin films of zirconium or zirconium-containing materials and the procedures stated between fourth and seventh step are performed in another chamber.
- the thin films of zirconium or zirconium-containing materials are exposed to oxygen or oxygen-containing gases in the presence of strong magnetic fields.
- the thin films of zirconium or zirconium-containing materials are essentially deposited onto a substrate in such a way that the content of the zirconium in the said thin films of zirconium or zirconium-containing materials is larger than 5 volume percent.
- the said thin films of zirconium or zirconium-containing materials have thicknesses between 0.01 and 100 micrometers.
- the said thin films of zirconium or zirconium-containing materials are glassy Zr-based alloys including ternary or more complex metallic glasses.
- the oxygen containing gas is selected from the list of gases including but not limited to oxygen, water vapor, carbon dioxide, carbon monoxide and nitric oxides.
- the magnetic field density is larger than 3 Gauss, preferably larger than 30 Gauss.
- the treatment time of said thin films of zirconium or zirconium-containing materials is larger than 10 s at the magnetic field density of 300 Gauss, and larger than 100 s at the magnetic field density of 30 Gauss.
- metallic glassy films were co-deposited on commercial Czochralski-grown, n-type Si(001 ) by unbalanced magnetron sputtering.
- High purity targets of Zr and Cu (99.8% and 99.99%, respectively) were fitted on the two magnetron guns, each one placed at 45° with respect to the substrate's plane.
- a small disc of high purity Nb foil 99.8% was fitted on the Zr target, covering about 10 percent of the sputtering ring.
- As sputtering gas was used high purity Argon (99.999%) which was leaked into the chamber achieving a working pressure of 4 Pa.
- the grown metallic glassy Zr 6 gCu 2 oNbn films were treated as oxidation templates for the production of zirconium oxide.
- the oxidation was performed in commercial borosilicate tube in which the metallic glassy films were placed, pumped by a rotary pump down to 1 Pa. By leaking industrial (commercial) oxygen the pressure was fixed at 40 Pa.
- An external metallic coil that surrounded the tube was used to generate oscillating magnetic field of industrial frequency 13.56 MHz.
- the magnetic field produced by the coil allowed for heating and oxidation of Zr-based Zr 6 9Cu 20 Nb metallic glassy films within some tens of seconds.
- FIG 2 it is shown the diffractogram of an oxidized Zr 6 9Cu 2 oNbn film as deduced by grazing incidence X-ray Diffraction method (XRD).
- XRD grazing incidence X-ray Diffraction method
- Pure tetragonal zirconia is formed after oxygen treatment of the Zr 6 9Cu 20 Nbn film supported by the rest non oxidized metallic glassy Zr 6 9Cu 20 Nb film placed on the substrate.
- the surface morphology of the produced tetragonal zirconia was further examined by Atomic Force Microscopy (AFM).
- the smooth surface of the as grown metallic glassy Zr69Cu20Nb.11 film was transformed to a quite rough surface after oxidation treatment, Figure 4.
- the nanostructured surface of the produced tetragonal zirconia film has higher active surface area, having as result the advantage of an enhanced catalytic efficiency compared to smooth film surfaces.
- the photo-catalytic activity of this embodiment was evaluated using aqueous solutions of the hazardous pollutants Di-tert butyl catechol (DTBC) and benzoic acid analytical grade (99% purity).
- the catalytic yield of this embodiment was examined by the direct comparison of the catalytic yield of commercial Degussa- P25 Ti0 2 photo-catalyst in powder form. This is because Degussa-P25 is known and well-studied due to its high photo-catalytic efficiency for the used chemical molecules [A.A. Ajmera et al., Chem. Eng. Technol. 25, 173 (2002); T. Velegraki et a!., Chem. Eng. J. 140, 15 (2008)].
- the detection of DTBC and benzoic acid was realized at 200 nm and 228 nm respectively.
- the photo-catalytic experiments were carried out in a Suntest XLS+ apparatus from Atlas (Germany) equipped with a vapor xenon lamp.
- the light source was jacked with special glass filters restricting the transmission of wavelengths to below 290 nm.
- the tap water cooling circuit was used to remove IR radiation preventing any heating of the suspension.
- Irradiation experiments were performed using DTBC or benzoic acid aqueous solution (0.5 mg L "1 ) and tetragonal zirconia film produced according to the methods of invention.
- Control irradiation experiments were performed using commercial Degussa-P25 TiO2 as catalyst (100 mg L "1 ).
- the solutions were mixed under stirring with the solid before and during the illumination.
- the suspensions were kept in the dark for 30 minutes, prior to illumination in order to reach adsorption equilibrium onto semiconductor surface. As the reactions progressed, at specific time intervals samples were withdrawn from the reactor for further analysis.
- Prior to photo-catalytic degradation direct photolysis experiments were conducted to evaluate their extent on DTBC and benzoic acid photo-catalytic degradation.
- HPLC High-Performance Liquid Chromatography
- the result of the methods of invention is tetragonal zirconium oxide in the form of thin films, which are stable at room temperature and the photo-catalytic activity of the said materials is superior comparing to the photo-catalytic activity of known materials.
- another advantage is its stability. This is very important since the surface of the catalyst, where the catalysis process takes place, can be cleaned after surface contamination that might occur over usage, without losing any active material or alteration of the surface composition and thus the photo- catalytic activity of the described embodiment.
Abstract
The present invention relates to a method of synthesizing tetragonal zirconia thin film material, said method comprising interaction of zirconium or zirconium-containing materials with a reaction gas comprising oxygen under elevated temperature and the influence of a magnetic field; a tetragonal zirconium material obtained thereby and its use in treatment of hazardous organic gases or liquids.
Description
Method for synthesis of tetragonal zirconia thin films suitable for catalytic devices
Field of the invention
The invention relates to methods for synthesizing stable tetragonal zirconium oxide in form of thin films with pre-selected surface morphologies using a thin film alloy. The invention also relates to methods for treating said alloy with a reaction gas in the presence of strong magnetic fields.
Background of the invention Zirconia and zirconia-based catalysts are widely used or studied for the use in many applications such as
- protective coatings [S. Heiroth et al., Acta Mater. 59, 2330 (201 1 )],
- high-k gate dielectric coatings [US8026161 ],
- optical coatings [Q.-L. Xiao et al. , Vacuum 83, 366 (2009)],
- catalytic coatings of vehicular exhaust gases [P. Alphonse and F. Ansart, J.
Colloid Interf. Sci. 658, 336 (2009); US5532198],
- electrolyte materials in oxide fuel cells [P. Amezaga-Madrid et al., J. Alloy Comp. 536S, S412 (2012)],
- optical waveguides [US7292766],
- semiconductor memory device of Zr02 dielectric films [US7491654].
Besides these applications zirconia exhibits good photo-catalytic activity; thus it is found in catalytic applications [J.-M. Herrmann, Top. Catal. 34, 49 (2005); US5532198; US0039814]. The most widely used transition metal oxides that exhibit high efficiency of photo-catalytic activity are the metastable crystal structures of the anatase Ti02 and the tetragonal Zr02 (zirconia).
The photo-catalytic activity of a solid is determined by two physical properties; the optical band gap, which is determined as the energy gap between the valence and the conduction bands and the crystal structure of the solid. The influence of the optical band gap in the photo-catalysis process is because the photo-catalytic activity may occur when a semiconductor solid is irradiated by a light source composed by photons with energy above the optical band gap of the solid, such as UV irradiation by a Xenon lamp or sun irradiation. In that case electrons from the valence band are excited to the conduction band and a pair of electron-hole (exciton) is created. Consequently, the electrons and the holes, which are separated by the band gap, create a polarization potential on the surface of the solid, which, if it is sufficient enough, causes the oxidation or the reduction of several chemical substances [US0039814]. The second physical property that determines the photo-catalytic efficiency of a catalytic solid is its crystal structure. This is because the crystal structure that is produced by specific electronic configuration has as a result the creation of different energy levels or states in the valence and conduction bands of the photo-catalytic solid, so even if two photo- catalytic solids with different crystal structures, i.e. monoclinic and tetragonal Zr02, they may have the similar values of their band gaps [Y. Gao et al., Chem. Mater. 16, 2615 (2004)], they will have different photo-catalytic efficiencies.
A method to examine and determine the photo-catalytic activity of a solid is the photo-catalytic activity in aqueous solutions. These measurements can be performed at constant temperature in a UV transparent tube, in which the catalyst is placed. The aqueous solution consisted of the molecules to be catalyzed is leaked in the tube. Prior to UV irradiation the system is left in the dark for 30 minutes in order to reach adsorption equilibrium onto the photo-catalyst surface. Thereafter, the photo-catalyst is irradiated by UV source, i.e. Xenon lamp filtered by any IR emission to avoid any heating of the photo-catalyst. The initial and the catalyzed solutions are characterized by liquid chromatography for the determination of the catalytic yield of the photo-catalyst.
The photo-catalytic activity differs for each photo-catalyst. The photo-catalytic studies have shown that zirconia exhibits high photo-catalytic efficiency as far as the catalysis of hazardous hydrocarbons, chlorides and nitrides is concerned (CH4, C2H6, HCHO, CH3OH, and HCOOH, CCI4, NOx [K.A. Bethke et al., Catal. Lett. 25, 37 (1994); C.-C. Lo et al., Sol. Energ. Mat. Sol. C. 91 , 1765 (2007); Y.-C. Chien et al., J. Hazard. Mater. 151 , 461 (2008)].
Zirconium oxide is found in different crystalline forms such as the monoclinic and tetragonal forms, and in the form of a thin film or powder. Regardless the form the stabilization of zirconium oxide is a difficult task. The knowledge on formation of zirconium oxide in thin solid films of improved photo-catalytic activity is limited, too. An important advantage of the zirconium oxide in the form of a thin film is ability to be deposited on various technological products and components, for example the industrial pipes, parts of vehicles, roofs and windows, what allows for photo- catalytic destruction of hazardous molecules that may be presented in the atmosphere or formed in industry. Another important advantage of the material in the form of a thin film is ability to be cleaned rather easily, especially when it becomes polluted before application, and the cleaning procedure does not cause a decrease of the catalytic activity. Cush losses are typical for zirconium oxide in the form of dust.
The technical problem solved by the methods of invention is the method for synthesizing stabile zirconium oxide in tetragonal form in the thin films, the material having superior photo-catalytic and being suitable for industrial production and use.
The solution of the technical problem should enable application of thin films of tetragonal zirconium oxide synthesized according to the methods of invention, the innovative method for synthesizing should be fast, economic, suitable for industrial applications and the material should have improved properties.
State of the art
The stabilization of the tetragonal zirconia, either in film or in powder form, is established by Zr02 growth or synthesis with aliovalent dopants, such as Y3+, Ca2+ and Na+ or even tetravalent Si +, Ce4+, Ge4+ and pentavalent Nb5+, Ta5+ dopants. The root for the stabilization involves the lower valence and larger dopants (in comparison with the Zr + ions) and it is believed to occur through the replacement of Zr4+ ions by aliovalent ions that lead to the creation of oxygen vacancies, which consequently force the solid in the formation of an eight coordinated polyhedron that is much closer to the symmetry of the tetragonal zirconia [J.C. Ray et al., J. Am. Ceram. Soc. 86, 514 (2003); J.C. Ray et al., Mater. Lett. 53, 145 (2002)] when dopants of lower valence and larger size are used (Nb, Ta, V) [G. Gopalakrishnan and S. Ramanathan, J. Mater. Sci. 46, 5768 (201 1 )]. The stabilization occurs for two reasons: a) the zirconia matrix is more positively charged and so the eight coordination symmetry is promoted and also the strong bonds of the Ta-0 or the Nb-O-Zr prohibit the reorientation of the atoms to form the stable monoclinic phase of Zr02 at room temperature; b) stabilization of tetragonal zirconia can be established also when small size and low valence dopants are used. This is because oxygen vacancies are created and so a smaller unit cell can be promoted forming the tetragonal phase, which has smaller volume unit cell than the monoclinic zirconia [V. Ramaswamy et al., Catal. Today 97, 63 (2004)].
Either in powder or in thin film form, the stabilization of the zirconia is still a challenging task and a field under research. Synthesis of stabilized zirconia at room temperature has been described in several papers and patents.
Tang et al [K. Tang et al. , J. Am. Chem. Soc. 130, 2676 (2008);] as well as Sato et al [K. Sato et al., J. Am. Chem. Soc. 132, 2538 (2010)] teach synthesis and stabilization of zirconium oxide at room temperature in powder form.
Chen et al [Scripta Mater. 68, 559 (2013)] described the synthesis of a thin film from a stable tetragonal zirconium oxide without dopants.
Sonderby et al [Surf. Coat. Tech. 206, 4126 (2012)] as well as Garcia et al [Thin Solid Films 370, 173 (2000)] described application of magnetron sputtering as well as deposition from the gas phase using metal-organic substances and obtained indirect growth of yttrium-stabilized zirconium oxide in the form of thin films.
Scherrer at al [Adv. Funct. Mater. 21 , 3967 (20 1 )] described formation of yttrium- stabilized zirconium oxide thin films by pyrolysis at 370°C. The film crystallized in a range of temperatures from 400 to 900°C. Fully crystallized thin films of yttrium- stabilized zirconium oxide were obtained by heating to 900°C or isothermal annealing at 600°C for at least 17 hours.
Lamas et al [Thin Solid Films 520, 4782 (2012)] described formation of yttrium- stabilized zirconium oxide thin films by magnetron sputtering from two sources. Piascik et al [J. Vac. Sci: Technol. A 23, 1419 (2005)] used radiofrequency discharge for magnetron sputtering of yttrium-stabilized zirconium oxide in the temperature range from 22 to 300°C and pressure range from 5 to 25 rnTorr in a gas mixture of argon and oxygen. The patent application US201 10319655 teaches a procedure for preparation of a material for catalyzers containing natural silicate in dust form and zirconium hydroxide in dust form. The mixture starts burning at temperatures above 620°C.
Patent US20060245999 teaches a procedure for synthesis of tetragonal zirconium, the procedure involves the following steps: (a) addition of zirconium precursor to precipitation substance, (b) exposure of first precipitate in liquids to temperatures higher than 80°C but lower than 120°C for one hour, so that a molten mixture forms, (c) drying the mixture in order to obtain a dry amorphous zirconium, and (d) firing the dry amorphous zirconium to final zirconium containing about 99.9% tetragonal zirconium.
Upper mentioned techniques have been applied in order to prepare tetragonal or cubic Zr20 films suitable for enforcement of dental ceramics, suitable for application as protective or optical coatings, for catalytic coatings on anodes of oxygen fuel cells as well as universal sensors of exhaust gases.
Various researches have been performed in order to enhance the photo-catalytic activity of tetragonal zirconium oxide.
Remarkable catalytic properties have been reported for the catalytic system of copper oxide supported tetragonal zirconia (CuO/zirconia) on the reduction of NOx and the steam-reforming of methanol [J. Luo et al. , Appl. Catal. A 423- 424, 121 (2012); H. Purnama et al. , Catal. Lett. 94, 61 (2004); K.A. Bethke et al., Catal. Lett. 25, 37 (1994)]. This high photo-catalytic efficiency is attributed to the creation of active sites on the catalytic support, zirconia in our case [G. Aguila et al., Appl. Catal. A 360, 98 (2009); R. Burch and A.R. Flambard, J. Catal. 78, 389 (1982)]. Also, the reported catalytic data from many studies showed that among other supported catalysts such as Ti02, Al203, Si02 and ZnO, the Zr02 has higher photo-catalytic efficiency. Studies on the photo-catalytic activity of copper supported Zr02, exhibited higher efficiency for tetragonal zirconia compared to the amorphous and monoclinic zirconia [P.D.L. Mercera et al. , Appl. Catal. 57, 127 (1990), G. Aguila et al. , Appl. Catal. B 77, 325 (2008); Z.-Y. Ma et al. , J. Mol. Catal. A 231 , 75 (2005)]. As G. Colon et al proposed, additional metallic elements enhance the catalytic activity of the photo-catalysts because they are acting as charge trapping sites that reduce the electron-hole recombination rate [G. Colon et al., Appl. Catal. B 67, 41 (2006)]. Furthermore, metallic elements that are used either for the stabilization of zirconia (Y, Nb, Fe) or as dopants (Mn, Cu) have been reported to enhance the photo-catalytic activity of zirconia [M. Alvarez et al, Appl. Catal B 73, 34 (2007) - F. Wyrwalski et al., J. Mater. Sci. 40, 933 (2005)]. The aliovalent dopants can be classified as donors and acceptors meaning that they act as valence substitutions or as lower valence ions, respectively, considering the ionic charge of the Zr + of zirconia [S.-Y. Chu et al., Integr. Ferroelectr. 58, 1293
(2003)]. Therefore, production of zirconia with Nb5+ and Cu2, + ionic charged dopants is expected to have enhanced photo-catalytic activity.
Despite the upper achievements the photo-catalytic activity of thin zirconium oxide films has not been investigated for the case minute quantities of niobium and copper oxide are added. Such research is time consuming, costly and requires application of various methods such as sol-gel, spinning deposition or pyrolysis for deposition of zirconium oxides and subsequent calcination.
Solution of the technical problem
The key feature of the invention is a method for synthesizing tetragonal zirconium oxide in the form of thin films comprising of two crucial steps. In the first step a glassy alloy is deposited onto a substrate by a suitable industrial-size method, the glassy alloy containing a large quantity of zirconium with addition of one or more elements selected from the group comprising copper, titanium and niobium, the selected materials serving for stabilization and improvement of the photo-catalytic properties. In the second step, oxidation is performed using oxygen or oxygen- containing gas at the presence of strong electromagnetic fields. The method is faster and cheaper than any other known method for synthesizing tetragonal zirconium oxide in the form of thin films. It can be realized in slightly adapted deposition chamber so no oxidation chamber is necessary. The synthesized tetragonal zirconium oxide in the form of thin films have improved properties as compared to known photo-catalytic materials and is useful for application of photo- catalytic devices, what has been proved by measuring catalytic activity for a couple of hazardous compounds, i.e. Di-tert butyl catechol (DTBC) and benzoic acid. The invention will be described to details referring to figures that show:
Figure 1 Amorphous structure of ternary metallic glassy (MG) Zr6gCu2oNbn
films prepared according to the methods of invention. (XRD)
Crystallographic structure of tetragonal zirconia materials (t-Zr02 on the Zr-Cu-Nb MG film) synthesized according to the methods of invention. (XRD)
The surface composition of the photo-catalyst (Zrs9Cu2oNb1i films) synthesized according to the methods of invention. (XPS) The surface morphology of tetragonal zirconium oxide materials synthesized according to the methods of invention. (AF )
Kinetic profiles of Di-tert butyl cathecol (DTBC) and benzoic acid (catalytic yield in ppm over mass of stable tetragonal zirconia film) synthesized according to a preferred embodiment of the invention. Six curves are presented. 1 - The initial concentration of organic substance per gram Zr02, 2 - 2-DTBC for the case of t-Zr02 film, 3 - benzoic acid for the case of t-Zr02 film, 4 - initial concentration of organic substance per gram Ti02, 5 - DTBC for the case of Ti02 dust, 6 - benzoic acid for the case of Ti02 dust. Kinetic profiles of Di-tert butyl cathecol (DTBC) and benzoic acid (catalytic yield in ppm over geometrical surface area of stable tetragonal zirconia film) synthesized according to a preferred embodiment of the invention. Six curves are presented. 1 - The initial concentration of organic substance per gram Zr02, 2 - 2- DTBC for the case of t-Zr02 film, 3 - benzoic acid for the case of t-ZrO2 film, 4 - initial concentration of organic substance per gram Ti02, 5 - DTBC for the case of Ti02 film, 6 - benzoic acid for the case of Ti02 film.
The aspect of this invention is a novel method for the production of photo-catalytic zirconia coatings by a two-step industrial scale process. Firstly, a proper Zr-based metallic glassy film is grown by an industrial scale deposition technique, which in this invention was chosen to be the magnetron sputtering. For the growth of Zr- based metallic glassy film the incorporation of Cu is crucial, due to its high glassy forming ability [A. Inoue et al., J. Non-Cryst. Solids 156-158, 473 (1993)]. For the
aim of this invention, the industrial scale growth of stabilized zirconia coatings with enhanced photo-catalytic activity, the incorporation of Cu in the oxidation metallic glassy film template is expected to increase the photo-catalytic efficiency of the proposed embodiment by the formation of CuO. Moreover, ternary Zr-based metallic glassy films with additional elements can be grown by magnetron sputtering. In this invention Nb was chosen for two reasons; a) it is a known stabilization element of zirconia and b) considering the ion Zr4+ it could enhance the photo-catalytic efficiency as a donor element. In the second step of the present invention, the metallic glassy films are used as templates for a fast (the order of magnitude is 10 seconds) treatment and low cost (no calcination procedures are needed) oxidation by oxygen in presence of a magnetic field. The Zr-based metallic glassy film template under a strong RF magnetic field is heated up to few hundred degrees of Celsius, while the atomic oxygen radicals (ATOX) oxidize the template. By this two-step process the production of zirconia thin film form stable at room temperature is possible. For these two described steps, the growth of the metallic glassy films and their oxidation, no in line deposition and oxidation chamber setup is needed, since the oxidation can be performed in the deposition chamber by minor modifications.
The methods of invention comprise the steps of:
- selecting a substrate and arranging the substrate into a high-vacuum treatment chamber;
- evacuating gas from said treatment chamber, thereby reducing the pressure in said treatment chamber to the range below 100 Pa;
- depositing thin films of zirconium or zirconium-containing materials onto substrates by vacuum deposition techniques;
- leaking oxygen or oxygen containing gas into the said high-vacuum chamber;
- applying an oscillating magnetic field to said treatment chamber;
- heating of said thin films of zirconium or zirconium-containing materials by induction due to the applied magnetic field;
- cooling of the thin films of zirconium or zirconium-containing materials down to room temperature.
It is also noted that in an industrial scale setup for the production of the metallic glassy and the tetragonal zirconia can be performed at the same chamber. That is easy to be constructed by placing, using an in vacuum transfer arm, the induction coil around the deposited metallic glassy Zr69Cu2oNbn film and leaking oxygen instead of argon. In another embodiment the said high-vacuum treatment chamber is used only for deposition of said thin films of zirconium or zirconium-containing materials and the procedures stated between fourth and seventh step are performed in another chamber.
In the preferred embodiment the thin films of zirconium or zirconium-containing materials are exposed to oxygen or oxygen-containing gases in the presence of strong magnetic fields. In further preferred embodiments the thin films of zirconium or zirconium-containing materials are essentially deposited onto a substrate in such a way that the content of the zirconium in the said thin films of zirconium or zirconium-containing materials is larger than 5 volume percent. In a further preferred embodiment the said thin films of zirconium or zirconium-containing materials have thicknesses between 0.01 and 100 micrometers. In a further preferred embodiment the said thin films of zirconium or zirconium-containing materials are glassy Zr-based alloys including ternary or more complex metallic glasses. In the further preferred embodiment the oxygen containing gas is selected from the list of gases including but not limited to oxygen, water vapor, carbon dioxide, carbon monoxide and nitric oxides. In preferred embodiments the magnetic field density is larger than 3 Gauss, preferably larger than 30 Gauss. In preferred embodiments the treatment time of said thin films of zirconium or zirconium-containing materials is larger than 10 s at the magnetic field density of 300 Gauss, and larger than 100 s at the magnetic field density of 30 Gauss.
In this embodiment, metallic glassy films were co-deposited on commercial Czochralski-grown, n-type Si(001 ) by unbalanced magnetron sputtering. A high
vacuum stainless steel chamber on which two magnetron sources were attached, was evacuated achieving a base pressure of 2 mPa, using a sequence of a turbomolecular and a rotary pumping system. High purity targets of Zr and Cu (99.8% and 99.99%, respectively) were fitted on the two magnetron guns, each one placed at 45° with respect to the substrate's plane. For the deposition of the ternary Zr-Cu-Nb metallic glassy films, a small disc of high purity Nb foil (99.8%) was fitted on the Zr target, covering about 10 percent of the sputtering ring. As sputtering gas was used high purity Argon (99.999%) which was leaked into the chamber achieving a working pressure of 4 Pa. Appling DC power of 60 Watt, which was shared at both magnetron guns, plasma generation was accomplished followed by sputtering of the materials and consequently by growth of metallic glassy films on the substrate, at room temperature.
The amorphous structure of the as grown ternary Zr69Cu20Nbn metallic glassy films, with the stoichiometry as deduced by means of Electron Dispersive Spectrometry (EDS), was determined by grazing incidence X-ray Diffraction measurements (XRD), Figure 1 . It is noted that the choice of the substrate does not influence the amorphous structure of the growing films, which is a crucial fact of this embodiment for wide area applications.
The grown metallic glassy Zr6gCu2oNbn films were treated as oxidation templates for the production of zirconium oxide. The oxidation was performed in commercial borosilicate tube in which the metallic glassy films were placed, pumped by a rotary pump down to 1 Pa. By leaking industrial (commercial) oxygen the pressure was fixed at 40 Pa. An external metallic coil that surrounded the tube was used to generate oscillating magnetic field of industrial frequency 13.56 MHz. The magnetic field produced by the coil allowed for heating and oxidation of Zr-based Zr69Cu20Nb metallic glassy films within some tens of seconds. In Figure 2 it is shown the diffractogram of an oxidized Zr69Cu2oNbn film as deduced by grazing incidence X-ray Diffraction method (XRD). Pure tetragonal zirconia is formed after oxygen treatment of the Zr69Cu20Nbn film supported by the rest non oxidized metallic glassy Zr69Cu20Nb film placed on the substrate.
The surface morphology of the produced tetragonal zirconia was further examined by Atomic Force Microscopy (AFM). The smooth surface of the as grown metallic glassy Zr69Cu20Nb.11 film was transformed to a quite rough surface after oxidation treatment, Figure 4. The nanostructured surface of the produced tetragonal zirconia film has higher active surface area, having as result the advantage of an enhanced catalytic efficiency compared to smooth film surfaces.
Although no detection of characteristic diffraction peaks of the Nb and Cu oxides were observed, X-ray Photoelectron spectroscopy revealed the presence of small amounts of Nb203 and CuO, Figure 3. These oxides are expected to enhance the photo-catalytic yield of the proposed catalyst produced by the specific method.
The photo-catalytic activity of this embodiment was evaluated using aqueous solutions of the hazardous pollutants Di-tert butyl catechol (DTBC) and benzoic acid analytical grade (99% purity). The catalytic yield of this embodiment was examined by the direct comparison of the catalytic yield of commercial Degussa- P25 Ti02 photo-catalyst in powder form. This is because Degussa-P25 is known and well-studied due to its high photo-catalytic efficiency for the used chemical molecules [A.A. Ajmera et al., Chem. Eng. Technol. 25, 173 (2002); T. Velegraki et a!., Chem. Eng. J. 140, 15 (2008)]. The detection of DTBC and benzoic acid was realized at 200 nm and 228 nm respectively.
As far as the irradiation procedure is concerned, the photo-catalytic experiments were carried out in a Suntest XLS+ apparatus from Atlas (Germany) equipped with a vapor xenon lamp. The light source was jacked with special glass filters restricting the transmission of wavelengths to below 290 nm. The tap water cooling circuit was used to remove IR radiation preventing any heating of the suspension.
Irradiation experiments were performed using DTBC or benzoic acid aqueous solution (0.5 mg L"1) and tetragonal zirconia film produced according to the methods of invention. Control irradiation experiments were performed using commercial Degussa-P25 TiO2 as catalyst (100 mg L"1).
In all experiments, the solutions were mixed under stirring with the solid before and during the illumination. The suspensions were kept in the dark for 30 minutes, prior to illumination in order to reach adsorption equilibrium onto semiconductor surface. As the reactions progressed, at specific time intervals samples were withdrawn from the reactor for further analysis. Prior to photo-catalytic degradation direct photolysis experiments were conducted to evaluate their extent on DTBC and benzoic acid photo-catalytic degradation. High-Performance Liquid Chromatography (HPLC) analysis was performed for the photo-degradation study in this embodiment. DTBC and benzoic acid concentrations were determined by a Dionex P680 HPLC chromatography equipped with a Dionex PDA -100 Photodiode Array Detector using a Discovery C-I8, (250 mm length * 4.6 mm ID: 5 pm particle size) analytical column from Supelco (Bellefonte, PA, USA). The HPLC mobile phase was a mixture of LC- grade water H2O pH 3 (adjusted with formic acid) (70) and acetonitrile (30) and 15:85 for benzoic acid and DTBC with a flow rate of 1 ml/min, respectively. Column temperature was set at 40 °C. The detection of DTBC and benzoic acid was realized at 200 nm and 228 nm respectively.
For DTBC, degradation of 54.89% is achieved within 180 min in the presence of zirconia catalysts. Turning on the benzoic acid, 20% degradation was observed after 180 min using UV light intensity 600 W/m2. A slight improvement in photo- catalytic degradation efficiency with UV intensity increasing (750 W/m2) has been observed.
Both investigated substrates were sufficiently degraded in aqueous titanium dioxide suspensions, after short irradiation time. When normalized per unit mass, Figure 5, or per unit surface area, Figure 6, the data demonstrated that tetragonal zirconia has by far superior photo-catalytic activity e.g. compared with Degussa P- 25 Ti02. More specifically the tetragonal zirconia film was able to achieve conversion of 22 ppm/gr of DTBC within 25 minutes under 600 W of UV-VIS
irradiation. For comparison Ti02 was able to convert 4.8ppm of DTBC, the effect being more visible when the photo-catalytic performance is normalized with respect to specific-surface-area of material as shown in Figure 6. The result of the methods of invention is tetragonal zirconium oxide in the form of thin films, which are stable at room temperature and the photo-catalytic activity of the said materials is superior comparing to the photo-catalytic activity of known materials. Besides the simplicity and the industrial scale method of the presented embodiment for the production of stabilized tetragonal zirconia in thin film form at room temperature, another advantage is its stability. This is very important since the surface of the catalyst, where the catalysis process takes place, can be cleaned after surface contamination that might occur over usage, without losing any active material or alteration of the surface composition and thus the photo- catalytic activity of the described embodiment.
Claims
1. Method for synthesizing tetragonal zirconium oxide thin film material, said method comprising two crucial steps, first one being deposition of a thin film of glassy alloy with a large zirconium content and addition of one or more elements selected from the group of copper, titanium and niobium, the second step being oxidation of thin films of said glassy alloy in the presence of oscillating magnetic field using oxygen or an oxygen-containing gas.
2. Method for synthesizing tetragonal zirconium oxide thin film material of claim 1 , wherein said thin films of zirconium or zirconium-containing materials are prepared following the steps of
- selecting a substrate for deposition of said thin film of glassy alloy and arranging the substrate into a high-vacuum treatment chamber;
- evacuating gas from said treatment chamber, thereby reducing the pressure in said treatment chamber to the range below 100 Pa;
- depositing thin films of zirconium or zirconium-containing materials onto substrates by vacuum deposition techniques;
- leaking oxygen or oxygen containing gas into the said high-vacuum chamber;
- applying an oscillating magnetic field to said treatment chamber;
- heating of said thin films of zirconium or zirconium-containing materials by induction due to the applied magnetic field;
- cooling of the thin films of zirconium or zirconium-containing materials down to room temperature.
3. Method for synthesizing tetragonal zirconium oxide thin film material of claims 1 and 2, wherein the treatments are performed in one or two chambers, wherein the treatments from the fourth line of claim 2 are performed in a separate chamber which is not said high-vacuum treatment chamber.
4. Method for synthesizing tetragonal zirconium oxide thin film material of claims from 1 to 3, wherein the said zirconium or zirconium-containing thin film is glassy alloy of zirconium and any other element selected from the group of copper, titanium and niobium.
5. Method for synthesizing tetragonal zirconium oxide thin film material of claims from 1 to 4, wherein the said zirconium or zirconium-containing thin film is prepared by any technique of vacuum deposition.
6. Method for synthesizing tetragonal zirconium oxide thin film material of claims from 1 to 5, wherein said thin films of zirconium or zirconium- containing materials are prepared by sputter deposition, preferably using magnetron sputtering devices.
7. Method for synthesizing tetragonal zirconium oxide thin film material of claims from 1 to 6, wherein said reaction gas comprising oxygen is selected from the list of gases including oxygen, air, carbon dioxide, nitric oxides, water vapor, or any mixture of these gases with any other gas.
8. Method for synthesizing tetragonal zirconium oxide thin film material of claims from 1 to 7, wherein said magnetic field has a density of at least 3 Gauss.
9. Method for synthesizing tetragonal zirconium oxide thin film material of claims from 1 to 8, wherein said contacting with reaction gas comprising oxygen under the influence of a magnetic field is for any period of time, preferably for the time period of from 1 seconds to 1000 seconds.
10. Method for synthesizing tetragonal zirconium oxide thin film material of claims from 1 to 9, wherein said contacting with reaction gas comprising oxygen is at a temperature of between 0°C and 800°C, preferably between 200°C and 800°C.
1 1. A tetragonal zirconium oxide material synthesized by a method of any one of claims from 1 to 10.
12. Use of tetragonal zirconium oxide material of claim 1 1 in treatment of hazardous organic gases or liquids.
13. Use of claim 12, wherein said treatment of hazardous organic gases or liquids is photo-catalytic destruction.
14. A product comprising a tetragonal zirconia material of claim 11.
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