KR101815999B1 - Fabrication method of whisker catalyst using galvanic displacement reaction and whisker catalyst - Google Patents
Fabrication method of whisker catalyst using galvanic displacement reaction and whisker catalyst Download PDFInfo
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- KR101815999B1 KR101815999B1 KR1020160008501A KR20160008501A KR101815999B1 KR 101815999 B1 KR101815999 B1 KR 101815999B1 KR 1020160008501 A KR1020160008501 A KR 1020160008501A KR 20160008501 A KR20160008501 A KR 20160008501A KR 101815999 B1 KR101815999 B1 KR 101815999B1
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- Prior art keywords
- substitution reaction
- whisker
- catalyst
- galvanic
- substrate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 34
- 238000006073 displacement reaction Methods 0.000 title description 3
- 238000006467 substitution reaction Methods 0.000 claims abstract description 98
- 239000000758 substrate Substances 0.000 claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 239000011133 lead Substances 0.000 claims description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 18
- 238000006722 reduction reaction Methods 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- -1 palladium ions Chemical class 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 4
- 239000001272 nitrous oxide Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/72—Copper
-
- B01J35/06—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to a process for preparing a galvanic replacement reaction solution by mixing a metal precursor and a dispersant (first step); And a step of immersing the metal substrate in the galvanic substitution reaction solution and forming an electrodeposited layer through a substitution reaction (second step). The present invention also provides a method for producing a whisker catalyst using a galvanic substitution reaction.
Description
The present invention relates to a method for producing a whisker catalyst using a galvanic substitution reaction and a whisker catalyst produced by the method.
Korean Patent Laid-Open Publication No. 10-2006-7012811 discloses a method for producing a whisker-like nanostructure, comprising the steps of providing at least one first catalyst particle on the surface of a substrate, A first step of growing a first nano-whisker; Providing at least one second catalyst particle on the periphery of the at least one first nano-whisker, and providing a second catalyst particle from the second catalyst particle to the second nano- And a second step of growing a nano-whisker.
The present invention relates to a method of manufacturing a metal catalyst having a high surface area by a one-step process by forming a whisker-like electrodeposited layer on a substrate surface through a galvanic substitution reaction.
The problems to be solved by the present invention are not limited to the above-mentioned problem (s), and another problem (s) not mentioned can be understood by those skilled in the art from the following description.
In order to solve the above problems, the present invention provides a method for producing a galvanic replacement reaction solution, comprising: (1) preparing a galvanic replacement reaction solution by mixing a metal precursor and a dispersant; And a step of immersing the metal substrate in the galvanic substitution reaction solution and forming an electrodeposited layer through a substitution reaction (second step). The present invention also provides a method for producing a whisker catalyst using a galvanic substitution reaction.
According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (a) preparing an etching solution capable of removing a native oxide film on a surface of a metal substrate; A metal precursor and a dispersing agent to prepare a galvanic substitution reaction solution (step b); (C) removing the natural oxide film on the surface of the metal substrate by dipping the metal substrate in the etching solution; And d) immersing the metal substrate in the galvanic substitution reaction solution to form an electrodeposited layer through a substitution reaction (step d).
In yet another embodiment of the present invention, there is provided a semiconductor device comprising: a substrate layer on which a cavity layer is formed; And an electrodeposited layer formed above the cavity layer.
In order to solve the above problems, the present invention provides a method for producing a galvanic replacement reaction solution, comprising: (1) preparing a galvanic replacement reaction solution by mixing a metal precursor and a dispersant; And a step of immersing the metal substrate in the galvanic substitution reaction solution and forming an electrodeposited layer through a substitution reaction (second step). The present invention also provides a method for producing a whisker catalyst using a galvanic substitution reaction.
According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (a) preparing an etching solution capable of removing a native oxide film on a surface of a metal substrate; A metal precursor and a dispersing agent to prepare a galvanic substitution reaction solution (step b); (C) removing the natural oxide film on the surface of the metal substrate by dipping the metal substrate in the etching solution; And d) immersing the metal substrate in the galvanic substitution reaction solution to form an electrodeposited layer through a substitution reaction (step d).
In yet another embodiment of the present invention, there is provided a semiconductor device comprising: a substrate layer on which a cavity layer is formed; And an electrodeposited layer formed above the cavity layer.
According to the present invention, when pitting corrosion of a metal substrate occurs as an oxidation reaction occurring during a galvanic substitution reaction, a charge transfer rate is increased so that a metal catalyst electrodeposition reaction occurring as a reduction reaction is introduced into a mass transfer rate region, A whisker-like catalyst electrodeposited in a direction perpendicular to the surface can be produced. Since the whisker type catalyst has a three-dimensional structure, the surface area where the reaction can occur is wider than that of the thin film type catalyst, thereby improving the catalytic activity.
Therefore, the conventional two-step process of carrying the metal catalyst on the surface of the substrate after preparing the substrate of the three-dimensional structure in order to produce the high surface area catalyst by using the whisker catalyst production method through the galvanic substitution reaction according to the present invention, It can be simplified to a one-step process in which the metal substrate is immersed in a solution containing a metal precursor and a dispersant.
When the whisker catalyst prepared according to the above-described method is used for the decomposition reaction of air pollutants such as nitrous oxide (N 2 O), it has an advantage that the durability of the catalyst can be increased and the catalytic activity can be maintained for a long time.
1 is a process flow diagram illustrating a method for preparing a whisker catalyst using a galvanic substitution reaction according to an embodiment of the present invention.
2 is a process flow diagram illustrating a method for producing a whisker catalyst using a galvanic substitution reaction according to another embodiment of the present invention.
FIG. 3 is a field emission scanning electron microscope (FE-SEM) photograph of a copper (Cu) substrate, which is a metal substrate according to an embodiment of the present invention, before proceeding with a galvanic substitution reaction.
FIG. 4 is a field emission scanning electron micrograph of a whisker catalyst prepared through a galvanic substitution reaction according to an embodiment of the present invention.
FIG. 5 is an X-ray diffraction pattern of a whisker catalyst prepared through a galvanic substitution reaction according to FIG.
6 is a field emission scanning electron microscope (SEM) image of a whisker catalyst prepared by a method for producing a whisker catalyst using a galvanic substitution reaction according to an embodiment of the present invention.
FIG. 7 is an X-ray diffraction analysis graph of a whisker catalyst prepared by a whisker catalyst preparation method using a galvanic substitution reaction according to an embodiment of the present invention.
FIG. 8 is a scanning electron microscope (SEM) image of a whisker catalyst prepared by a method for producing a whisker catalyst using a galvanic substitution reaction according to another embodiment of the present invention.
9 is a graph showing the activity and durability of a whisker catalyst prepared through a galvanic substitution reaction according to an embodiment of the present invention.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving it will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.
The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.
In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.
1 is a process flow diagram illustrating a method for preparing a whisker catalyst using a galvanic substitution reaction according to an embodiment of the present invention.
Referring to FIG. 1, a method for preparing a whisker catalyst using a galvanic substitution reaction according to the present invention comprises: (1) preparing a galvanic substitution reaction solution by mixing a metal precursor and a dispersing agent; And a step of immersing the metal substrate in the galvanic substitution reaction solution and forming an electrodeposited layer through a substitution reaction (second step).
When the catalyst is electrodeposited on the substrate using the galvanic substitution reaction, the substrate may be immersed in a solution containing the catalyst metal ions to spontaneously support the catalyst metal on the substrate without external energy supply, It is possible to reduce the amount of noble metal supported in the field where a noble metal catalyst such as a fuel cell or a greenhouse gas decomposition is used.
When the electrodeposited layer is formed through the substitution reaction by preparing the galvanic substitution reaction solution and immersing the metal substrate in the galvanic substitution reaction solution, the electrodeposition layer is formed into a whisker-like three-dimensional structure, The conventional two step process of carrying the metal catalyst on the surface of the substrate after preparation of the substrate can be simplified to a one step process in which the general metal substrate is immersed in the solution containing the metal precursor and the dispersant.
In the step of forming the electrodeposited layer through the substitution reaction, pitting corrosion may be generated on the surface of the metal substrate.
The formula The reaction is a type of oxidation reaction of the galvanic replacement reaction, a general oxidation of the copper substrate is Cu → Cu 2 + + 2e - proceeds to - → CuCl 2 - - + e Cu + 2Cl according whereas in the formula the reaction do. Therefore, when chloride ion (Cl - ) is present in the galvanic substitution reaction solution, an official reaction may occur.
2 is a process flow diagram illustrating a method for producing a whisker catalyst using a galvanic substitution reaction according to another embodiment of the present invention.
Referring to FIG. 2, the present invention provides a method for manufacturing a semiconductor device, comprising: (a) preparing an etching solution capable of removing a native oxide film on a surface of a metal substrate; Preparing a galvanic replacement reaction solution by adding a metal precursor and a dispersant (step b); (C) removing the natural oxide film on the surface of the metal substrate by dipping the metal substrate in the etching solution; And d) immersing the metal substrate in the galvanic substitution reaction solution to form an electrodeposited layer through a substitution reaction (step d).
In another embodiment of the present invention, an etchant solution can be used to remove the self-assembled film that may be formed on the surface of the metal substrate in advance.
When the natural oxide film is removed, the galvanic substitution reaction may be more actively performed. However, even if the natural oxide film removing step is not performed using the etching solution, a whisker-type three-dimensional structure electrodeposition layer may be formed through the galvanic substitution reaction And removing the native oxide film through the etching solution. However, the present invention is not limited thereto.
The metal substrate may include at least one of copper (Cu), gold (Au), lead (Pb), nickel (Ni), rhodium (Rh), ruthenium (Ru), manganese (Mn), molybdenum (Mo) (Ag), iridium (Ir), tin (Sn), iron (Fe), cobalt (Co), chromium (Cr), titanium (Ti) And palladium (Pd).
A cavity may not be formed well during the galvanic substitution reaction other than the metal substrate.
The etching solution for native oxide removal of the metal substrate surface, hydrogen peroxide (H 2 O 2), citric acid [HOC (COOH) (CH 2 COOH) 2], hydrofluoric acid (HF), potassium hydroxide (KOH), acetate (CH 3 CO 2 H), oxalic acid (HO 2 CCO 2 H), and sulfuric acid (H 2 SO 4 ).
The etching solution may be prepared to remove the natural oxide film on the surface of the metal substrate (S100).
It may be difficult to etch the native oxide film on the surface of the selected metal substrate other than the etching solution.
In the first or b step, the galvanic substitution reaction solution may be prepared by mixing a metal precursor and a dispersing agent (S10, S200).
The metal precursor may be at least one selected from the group consisting of Cu, Au, Pb, Ni, Rh, Ru, Mn, (Ag), iridium (Ir), tin (Sn), iron (Fe), cobalt (Co), chromium (Cr), titanium (Ti) And palladium (Pd).
The precursor should use a metal precursor having a positive standard reduction potential value as compared with a metal used as a metal substrate and may be subjected to a galvanic substitution reaction using a standard reduction potential difference as a driving force. A substitution reaction may not occur.
There may arise a problem that galvanic substitution reaction does not occur well except for the metal precursor.
The dispersant may be at least one selected from the group consisting of perchloric acid (HClO 4 ), sodium cyanide (NaCN), sodium citrate (Na 3 C 6 H 5 O 7 ), thiourea (SC (NH 2 ) 2 ), acetic acid (C 2 H 4 O 2 ) Ammonia water (NH 4 OH), ethylenediaminetetraacetic acid (EDTA), hydrochloric acid (HCl), ammonium chloride (NH 4 Cl), nitric acid (HNO 3 ), hexamethylenetetramine (C 6 H 2 N 4 ) H 2 SO 4 ), and the like.
The dispersant forms a coordination bond with palladium ions, and plays a role of helping the palladium ions to be stably dispersed in the solution without being precipitated. Depending on the kind of the dispersant, the coordination bond strength with palladium changes. When the strength is too strong, palladium electrodeposition as a result of the galvanic substitution reaction is difficult to occur. If the dispersant is too weak, palladium precipitation may occur, Should be used.
On the other hand, the galvanic replacement reaction solution is fluoride ion (F -), which could lead to the official reaction of the substrate 1 is selected from the group consisting of chlorine ion (Cl -), bromide ion (Br - -), and an iodine ion (I) Or more species.
In addition to the above ions, the rate of the oxidation reaction and the rate of the reduction reaction can not be controlled in the galvanic substitution reaction, so that a problem that a whisker-like electrodeposited layer can not be formed on the metal substrate may occur.
The metal substrate may be immersed in the etching solution prepared in the step (a) to remove the natural oxide film on the surface of the metal substrate (S300).
In the second or d step, the immersion time of the metal substrate may be 10 to 3600 seconds.
When the immersion time is shorter than 10 seconds, the electrodeposited layer formed as a result of galvanic substitution reaction can not grow in a whisker form due to a short reaction time. When the immersion time exceeds 3600 seconds, There is a problem that whisker catalyst on the surface of the metal substrate is also lost together with the metal substrate completely dissolved in the solution by the oxidation reaction.
The metal substrate on which the natural oxide film has been removed may be immersed in the galvanic substitution reaction solution to form an electrodeposited layer through a substitution reaction (S400).
Here, as the oxidation reaction occurring during the galvanic substitution reaction, an official reaction of the metal substrate occurs. As a result, the charge transfer rate of the reduction reaction becomes sufficiently high, so that the metal catalyst electrodeposition reaction enters the mass transfer rate region, and a whisker-like electrodeposited layer in which the metal catalyst is vertically deposited on the substrate surface can be formed.
The reaction temperature of the galvanic substitution reaction is preferably 10 to 90 ° C.
When the reaction temperature is lower than 10 ° C, the reaction rate is very slow. Therefore, the reaction time required for producing a whisker catalyst of a predetermined size is long and the process efficiency is lowered. When the reaction temperature is higher than 90 ° C, There is a problem in that whisker catalyst on the surface of the metal substrate disappears together with the metal substrate completely dissolved by the oxidation reaction during the reaction time.
According to another aspect of the present invention, there is provided a whisker catalyst comprising a substrate layer and an electrodeposited layer.
The substrate layer may be formed with a cavity layer on its surface.
The electrodeposited layer may be formed on top of the cavity layer.
Also, the electrodeposited layer is a whisker-type three-dimensional structure, and the electrodeposited layer may be formed on the substrate layer with an average thickness of 300 nm to 6 μm.
In the above range, it is possible to exhibit high durability for a long period of time in the gas reduction decomposition reaction.
The substrate layer may have an average thickness of 60 nm to 1 mm.
When the average thickness of the substrate layer is less than 60 nm, the substrate is dissolved by the oxidation reaction during the galvanic substitution reaction, and the substrate supporting the whisker-like electrodeposited layer is dissolved before the reaction is completed The whisker catalyst may be lost.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention.
< Example 1> Galvanic Through the substitution reaction Whisker Catalyst preparation
Before the galvanic substitution reaction, the copper substrate was immersed in a solution of 20.4 mM citric acid [HOC (COOH) (CH 2 COOH) 2 ] and 35.6 mM potassium chloride (KOH) And immersed for 2 minutes. The reaction proceeded at 25, and the washing process was carried out immediately after the reaction by immersing in distilled water twice for 10 seconds.
The whisker catalyst was synthesized by immersing the copper substrate from which the natural oxide film on the substrate surface was removed in a galvanic substitution reaction solution for 30 minutes. The galvanic substitution reaction solution was prepared by adding 3 mM palladium chloride (PdCl 2 ) as a metal precursor and 0.1 M perchloric acid (HClO 4 ) as a dispersant. The galvanic substitution reaction proceeded at 25, and the washing process was carried out immediately after the reaction by soaking in distilled water twice for 10 seconds.
< Experimental Example 1> Whisker Catalyst properties
FIG. 3 is a photograph of a field emission scanning electron microscope (FE-SEM, S4800, Hitachi) before proceeding a galvanic substitution reaction of a Cu substrate which is a metal substrate according to an embodiment of the present invention.
Referring to FIG. 3, it was confirmed that a native oxide film of a copper substrate was formed.
FIG. 4 is a field emission scanning electron micrograph of a whisker catalyst prepared through a galvanic substitution reaction according to an embodiment of the present invention.
4, a copper substrate is immersed in an etching solution for removing a native oxide film containing citric acid [HOC (COOH) (CH 2 COOH) 2 ] and potassium hydroxide (KOH) according to FIG. 2 to form a natural oxide film And then a copper substrate is immersed in a galvanic substitution reaction solution containing a palladium chloride (PdCl 2 ) metal precursor and a perchloric acid (HClO 4 ) dispersant, a three-dimensional whisker-like electrodeposited layer is formed on the copper substrate .
During the galvanic substitution reaction, copper having a low standard reduction potential is converted into copper ion through oxidation to dissolve in the substrate, and palladium ions having a standard reduction potential higher than copper are electrodeposited from the palladium chloride precursor through the reduction reaction Respectively.
FIG. 5 is an X-ray diffraction pattern graph of a whisker catalyst prepared through a galvanic substitution reaction according to an embodiment of the present invention.
Referring to FIG. 5, it was confirmed that the produced whisker catalyst was composed of a palladium-copper mixed metal.
< Experimental Example 2> Galvanic Depending on the ions in the displacement reaction solution Electrodeposited layer formation
In order to confirm the formation of electrodeposition layer depending on the type of ions in the solution during the galvanic substitution reaction, a galvanic substitution reaction solution was prepared by changing the salt added.
Solution 1 was prepared by mixing 3 mM PdCl 2 and 0.1 M HClO 4 , and
In each solution, the reaction temperature was maintained at 25 ℃ and the copper substrate was immersed and reacted for 30 minutes to confirm formation of an electrodeposited layer by galvanic substitution reaction.
FIG. 6 is a field emission electron micrograph of a whisker catalyst prepared by a whisker catalyst production method using a galvanic substitution reaction according to an embodiment of the present invention.
FIG. 6 (a) shows a galvanic substitution reaction in solution 1, and FIG. 6 (b) shows a galvanic substitution reaction in
Referring to the drawings, a cavity is formed in the copper substrate by an oxidation reaction occurring during a galvanic substitution reaction, and a whisker-like electrodeposited layer is formed by a reduction reaction.
Referring to FIG. 6 (b), it is difficult to form a whisker-like electrodeposited layer from sulfate ions other than chlorine ions, so that the oxidation reaction rate and the reduction reaction rate of the galvanic substitution reaction vary depending on the type of anions contained in the Pd salt Respectively.
When the anion contained in the above-mentioned galvanic substitution reaction solution is Cl - , the oxidation reaction of copper is promoted more than the SO 4 2- ion to promote the reduction reaction of palladium. This makes it possible to increase the concentration gradient of palladium ions on the surface of the substrate, It was confirmed that it could grow in whisker form.
In addition, when the anion was Cl - , diffusion rate of palladium ion was slower than that of SO 4 2- ion, and the electrodeposited layer could grow in the form of whiskers.
FIG. 7 is an X-ray diffraction analysis graph of a whisker catalyst prepared by a whisker catalyst preparation method using a galvanic substitution reaction according to an embodiment of the present invention.
Fig. 7 (a) shows a galvanic substitution reaction in solution 1, and Fig. 7 (b) shows a galvanic substitution reaction in
Referring to FIG. 7, when the solution 1 (PdCl 2 ) was used, an electrodeposited layer composed of Pd and PdCu was formed. However, when the solution 2 (PdSO 4 ) solution was used, it was confirmed that an electrodeposited layer composed of PdCu was formed.
On the other hand, in order to confirm whether whisker catalysts were formed by using a galvanic substitution reaction in other salts including chlorine ions, 3 mM K 2 PtCl 4 and 0.1 M HClO 4 Were mixed to prepare
FIG. 8 is a scanning electron microscope (SEM) image of a whisker catalyst prepared by a method of preparing a whisker catalyst using a galvanic substitution reaction according to another embodiment of the present invention.
Fig. 8 (a) shows the result of the galvanic substitution reaction in the
Referring to Figure 8, PdCl 2 In addition, when a galvanic substitution reaction is carried out using Pt or Au salts containing Cl - ions, it is confirmed that a whisker electrodeposition layer can be formed, and a whisker electrodeposition layer is formed when the added anion is chlorine ion .
< Experimental Example 3> Whisker Reduction decomposition of gas by catalyst
9 is a graph showing the activity and durability of a whisker catalyst prepared through a galvanic substitution reaction according to an embodiment of the present invention.
The catalytic activity and durability of the whisker catalyst and the commercial palladium catalyst prepared through the galvanic substitution reaction were evaluated by the time zone current method for the nitrous oxide (N 2 O) gas reduction decomposition reaction.
In the time - domain current method, a whisker catalyst and a commercial palladium catalyst were used as a working electrode, a platinum electrode as a counter electrode, and a three - electrode cell having a saturated calomel electrode as a reference electrode. 0.3 MK 2 SO 4 was used as the electrolyte, and nitrous oxide was dissolved in the electrolyte for 30 minutes at 100 ml / min before the time zone current method. To perform the time zone current method, 0.9 V was applied for 30 minutes so that a nitrous oxide reduction reaction occurs at the working electrode. At this time, the internal temperature of the reactor was adjusted to 25 캜.
As a result of the time - domain current analysis, whisker catalysts maintained high current density and less current density reduction ratio than commercial palladium catalysts during analytical time.
Therefore, since the catalyst prepared by the whisker catalyst production method using the galvanic substitution reaction according to the present invention has a three-dimensional structure, the surface area where the reaction can occur is wider than that of the thin film type catalyst, thereby improving the catalytic activity.
Also, in order to manufacture a high surface area catalyst, a conventional two-step process of carrying a metal catalyst on the surface of a substrate after preparing a substrate of a three-dimensional structure is a one-step process of immersing a general metal substrate in a solution containing a metal precursor and a dispersant Can be performed.
Although the method for producing a whisker catalyst using a galvanic substitution reaction according to the present invention and the whisker catalyst prepared therefrom have been described, various modifications may be made without departing from the scope of the present invention. Do.
Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.
It is to be understood that the foregoing embodiments are illustrative and not restrictive in all respects and that the scope of the present invention is indicated by the appended claims rather than the foregoing description, It is intended that all changes and modifications derived from the equivalent concept be included within the scope of the present invention.
Claims (13)
And a step of immersing the metal substrate in the galvanic substitution reaction solution and forming an electrodeposited layer through a substitution reaction (Step 2).
A metal precursor and a dispersing agent to prepare a galvanic substitution reaction solution (step b);
(C) removing the natural oxide film on the surface of the metal substrate by dipping the metal substrate in the etching solution; And
And d) immersing the metal substrate in the galvanic substitution reaction solution to form an electrodeposited layer through a substitution reaction (step d).
Wherein the electrodeposited layer has a whisker-like three-dimensional structure and has an average thickness of 300 nm to 6 占 퐉.
The metal substrate may include at least one of copper (Cu), gold (Au), lead (Pb), nickel (Ni), rhodium (Rh), ruthenium (Ru), manganese (Mn), molybdenum (Mo) (Ag), iridium (Ir), tin (Sn), iron (Fe), cobalt (Co), chromium (Cr), titanium (Ti) And palladium (Pd). The method for producing a whisker catalyst according to claim 1,
The etching solution is for removing a natural oxide film on the surface of the metal substrate. The etching solution is a solution of hydrogen peroxide (H 2 O 2 ), citric acid [HOC (COOH) (CH 2 COOH) 2 ], hydrofluoric acid (HF), potassium hydroxide Wherein the catalyst is at least one selected from the group consisting of acetic acid (CH 3 CO 2 H), oxalic acid (HO 2 CCO 2 H), and sulfuric acid (H 2 SO 4 ).
The metal precursor may be at least one selected from the group consisting of Cu, Au, Pb, Ni, Rh, Ru, Mn, (Ag), iridium (Ir), tin (Sn), iron (Fe), cobalt (Co), chromium (Cr), titanium (Ti) And palladium (Pd). The method for producing a whisker catalyst according to claim 1,
The dispersant may be at least one selected from the group consisting of perchloric acid (HClO 4 ), sodium cyanide (NaCN), sodium citrate (Na 3 C 6 H 5 O 7 ), thiourea (SC (NH 2 ) 2 ), acetic acid (C 2 H 4 O 2 ) Ammonia water (NH 4 OH), ethylenediaminetetraacetic acid (EDTA), hydrochloric acid (HCl), ammonium chloride (NH 4 Cl), nitric acid (HNO 3 ), hexamethylenetetramine (C 6 H 2 N 4 ) H 2 SO 4 ). The method for producing a whisker catalyst according to claim 1,
The galvanic replacement reaction solution is fluoride ion (F -), which could lead to the official reaction of a substrate one type of compound selected from the group consisting of chlorine ion (Cl -), bromide ion (Br - -), and an iodine ion (I) Of the total amount of the whisker catalyst.
Wherein the time for immersing the metal substrate in the galvanic substitution reaction solution is 10 to 3600 seconds.
Wherein the reaction temperature of the substitution reaction is 10 to 90 ° C.
And an electrodeposited layer formed above the cavity layer,
Wherein the electrodeposited layer is a whisker-type three-dimensional structure and is formed on the substrate layer in an average thickness of 300 nm to 6 탆.
Wherein the substrate layer has an average thickness of 60 nm to 1 mm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2236203A1 (en) | 1972-07-24 | 1974-02-07 | Suwa Seikosha Kk | Controlling whisker growth - by means of non-uniformly dispersed catalyst |
| JP2015525675A (en) | 2012-08-10 | 2015-09-07 | ジョンソン、マッセイ、フュエル、セルズ、リミテッドＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｆｕｅｌ Ｃｅｌｌｓ Ｌｉｍｉｔｅｄ | Method for preparing a catalyst material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2236203A1 (en) | 1972-07-24 | 1974-02-07 | Suwa Seikosha Kk | Controlling whisker growth - by means of non-uniformly dispersed catalyst |
| JP2015525675A (en) | 2012-08-10 | 2015-09-07 | ジョンソン、マッセイ、フュエル、セルズ、リミテッドＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｆｕｅｌ Ｃｅｌｌｓ Ｌｉｍｉｔｅｄ | Method for preparing a catalyst material |
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| J. of Advanced Ceramics 2015, 4(3), pp. 232-236 |
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