WO2006038476A1 - Bain de sel fondu, précipité obtenu en employant le bain de sel fondu, méthode d’obtention d’un composé métallique et composé métallique - Google Patents

Bain de sel fondu, précipité obtenu en employant le bain de sel fondu, méthode d’obtention d’un composé métallique et composé métallique Download PDF

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Publication number
WO2006038476A1
WO2006038476A1 PCT/JP2005/017510 JP2005017510W WO2006038476A1 WO 2006038476 A1 WO2006038476 A1 WO 2006038476A1 JP 2005017510 W JP2005017510 W JP 2005017510W WO 2006038476 A1 WO2006038476 A1 WO 2006038476A1
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Prior art keywords
salt bath
molten salt
precipitate
density
atomic
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PCT/JP2005/017510
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English (en)
Japanese (ja)
Inventor
Koji Nitta
Shinji Inazawa
Kazunori Okada
Toshiyuki Nohira
Hironori Nakajima
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Sumitomo Electric Industries, Ltd.
Kyoto University
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Application filed by Sumitomo Electric Industries, Ltd., Kyoto University filed Critical Sumitomo Electric Industries, Ltd.
Priority to US11/664,095 priority Critical patent/US20080105553A1/en
Priority to DE112005002435.0T priority patent/DE112005002435B4/de
Priority to CN2005800335362A priority patent/CN101035930B/zh
Priority to JP2006539225A priority patent/JP4785141B2/ja
Publication of WO2006038476A1 publication Critical patent/WO2006038476A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/022—Electroplating of selected surface areas using masking means

Definitions

  • the present invention relates to a molten salt bath, a precipitate obtained using the molten salt bath, a method for producing a metal product, and a metal product.
  • metals such as tungsten and molybdenum (refractory metals) in groups IVA to VIA and 4 to 6 in the periodic table are excellent in heat resistance and corrosion resistance. Can be used in the above-mentioned fine metal products, it is possible to produce fine metal products with excellent heat resistance and durability.
  • Non-Patent Document 1 P. M. COPHAM, D. J. FRAY, "Selecting an optimum electrolyte for zinc chloride electrolysis", JOURNAL OF APPLIED
  • Non-Patent Document 2 M. Masuda, H. Takenishi, and A. Katagiri, "Electrodep osition of Tungsten and Related Voltammetric Study in a Basic Z nC12-NaCl (40-60 mol%) Melt", Journal of The Electrochemical Soc iety, 148 (1), 2001, p. C59 -C64
  • Non-Patent Document 3 Satoshi Katagiri, “Electrodeposition of tungsten in ZnC12—NaCl and ZnBr2—NaBr molten salts”, Molten salt and high temperature chemistry, Vol. 37, No. 1, 1994, p.2
  • Non-Patent Document 4 Nikonova IN, Pavlenko SP, Bergman AG, "Polytherm of the ternary system NaCl—KC1-ZnC12", Bull. Acad. Sci. URSS, Classe sci. Chim. (1941), p. 391—400
  • An object of the present invention is to provide a molten salt bath with high purity, high density and high density and capable of obtaining a smooth surface refractory metal precipitate, and an analysis obtained using the molten salt bath.
  • the present invention relates to at least one selected from the group force consisting of chlorine, bromine and iodine, and zinc.
  • a molten salt bath containing at least two alkali metals and fluorine.
  • the molten salt bath of the present invention may contain oxygen.
  • the molten salt bath of the present invention has a group force of tungsten, chromium, molybdenum, tantalum, titanium, zirconium, vanadium, hafnium, and niobium force.
  • the molten salt bath of the present invention comprises at least two selected from the group force consisting of sodium, potassium, and cesium as alkali metals, at least one of chlorine and bromine, zinc, and fluorine. obtain.
  • the zinc content is 14 atomic% or more and 30 atomic% or less of the entire molten salt bath.
  • the zinc content is 17 atomic% or more and 25 atomic% or less of the entire molten salt bath.
  • the fluorine content is 0.1 atom of the entire molten salt bath.
  • the present invention is a precipitate obtained using the molten salt bath described above.
  • the precipitate of the present invention is preferably deposited in a state where the molten salt bath contains 0.01 atomic% or more of oxygen.
  • the arithmetic average roughness Ra FIS B0601-1994) of the surface of the precipitate of the present invention is preferably 3 / z m or less.
  • the relative density of the precipitate of the present invention is preferably 85% or more.
  • the present invention provides a process for forming a resist pattern on a conductive substrate to expose a part of the conductive substrate, and the conductive substrate on which the resist pattern is formed in the molten salt bath described in any of the above. It is a method for producing a metal product, which includes a step of immersing and a step of depositing a metal from a molten salt bath in an exposed portion of a conductive substrate.
  • the temperature of the molten salt bath may be 250 ° C. or less.
  • the present invention is a metal product manufactured by using the above metal product manufacturing method.
  • a molten salt bath that is capable of obtaining a precipitate of a refractory metal having a high purity, a high density, and a high density and having a smooth surface, and an analysis obtained using the molten salt bath.
  • a product, a method for manufacturing a metal product, and a metal product can be provided.
  • FIG. 1 is a schematic configuration diagram illustrating an example of a method for obtaining a precipitate using the molten salt bath of the present invention.
  • the present invention is a molten salt bath containing at least one selected from the group force consisting of chlorine, bromine and iodine, zinc, at least two alkali metals, and fluorine.
  • the molten salt bath of the present invention contains at least two of lithium, sodium, potassium and cesium as alkali metals.
  • the form in the molten salt bath of at least one, zinc, at least two alkali metals and fluorine, etc., which also selected the group power consisting of chlorine, odor, and iodine, constituting the molten salt bath of the present invention is particularly preferable.
  • these components may exist as ions in the molten salt bath, or may exist in a complexed state.
  • the above-mentioned components constituting the molten salt bath of the present invention can be detected by performing ICP spectroscopic analysis (ICP spectroscopic analysis) on a sample in which the molten salt bath of the present invention is dissolved in water.
  • the molten salt bath of the present invention may contain oxygen in addition to the above components.
  • oxygen When the molten salt bath of the present invention contains oxygen, it tends to be able to obtain precipitates with higher purity, higher density and higher density and with a smoother surface.
  • the form of oxygen in the molten salt bath of the present invention is not particularly limited, and may be present, for example, as an ion, in a state of forming a complex, or in an acidic state.
  • the presence of oxygen in the molten salt bath of the present invention can be confirmed by using an inert gas melting infrared absorption method for the molten salt bath of the present invention.
  • the inert gas melting infrared absorption method is performed, for example, as follows. First, a molten salt bath is accommodated in a carbon crucible in a helium gas atmosphere, and oxygen is generated from the molten salt bath by heating the carbon crucible. This oxygen then reacts with the carbon in the carbon crucible to produce carbon monoxide and carbon dioxide. Next, infrared rays are irradiated in the atmosphere containing the generated carbon monoxide and carbon dioxide. Finally, the presence and content of oxygen in the molten salt bath can be confirmed by investigating the attenuation of infrared rays generated by the absorption of carbon monoxide and carbon dioxide in the atmosphere.
  • the molten salt bath of the present invention may contain at least one selected from the group consisting of tungsten, chromium, molybdenum, tantalum, titanium, zirconium, vanadium, hafnium, and niobium. These metals are refractory metals in the Periodic Tables Group IVA to Group VIA and Groups 4 to 6. Including this refractory metal When electrolysis is carried out using a bright molten salt bath, it is possible to obtain precipitates with high purity, high density and high density mainly composed of these refractory metals and with a smooth surface. it can.
  • tungsten, chromium, molybdenum, tantalum, titanium, zirconium, vanadium, hafnium or niobium in the molten salt bath of the present invention is not particularly limited. May be
  • the content of the refractory metal in the molten salt bath should be 0.04 atomic% or more when the total components constituting the molten salt bath are 100 atomic%. This is preferred from the viewpoint of obtaining a dense refractory metal precipitate with a smooth surface.
  • the higher the refractory metal content in the molten salt bath the higher the current density, the more refractory metal precipitates can be obtained, but the refractory metal content is higher. As the number increases, the melting point of the molten salt bath rises, and it is necessary to raise the temperature of the molten salt bath during electrolysis.
  • the content of the refractory metal increases, for example, it becomes impossible to perform electrolysis by immersing a conductive substrate on which a resist pattern having a low melting point, such as resin, having a material strength is immersed in a molten salt bath. Therefore, the content of the refractory metal is preferably set appropriately according to the purpose.
  • the presence and content of the refractory metal in the molten salt bath of the present invention should be detected and calculated by performing ICP spectroscopic analysis on a sample in which the molten salt bath of the present invention is dissolved in water. Can do.
  • the purpose of the present invention is to obtain a refractory metal precipitate having a high purity, a high density and a high density and a smooth surface. It goes without saying that precipitates other than kutry metal may be obtained.
  • the molten salt bath of the present invention includes at least two selected from the group force consisting of sodium, potassium, and cesium as the alkali metal, at least one of chlorine and bromine, zinc, and fluorine. It is preferable to consist of. In this case, precipitates with higher purity, higher density, and higher density and having a smooth surface tend to be obtained.
  • at least two selected group powers consisting of sodium, potassium and cesium at least one of chlorine and bromine, and components inevitably contained other than zinc and fluorine.
  • the zinc content in the molten salt bath of the present invention is 14 atomic% or more and 30 atomic% or less of the entire molten salt bath. Is more preferred. If the zinc content is less than 14 atomic% of the total molten salt bath or more than 30 atomic%, high purity, high density and smooth deposits on the surface tend not to be obtained. In addition, when the zinc content is not less than 17 atomic% and not more than 25 atomic% of the entire molten salt bath, the temperature of the molten salt bath can be reduced to 250 ° C or lower.
  • the metal product can be produced by electric heating at a low temperature of the molten salt bath of 250 ° C or lower.
  • the zinc content in the molten salt bath of the present invention can be detected by performing ICP spectroscopic analysis on a sample obtained by dissolving the molten salt bath of the present invention in water.
  • the conductive substrate for example, a substrate made of a simple metal or an alloy, or a substrate in which a conductive metal or the like is attached on a nonconductive base material such as glass is used. it can.
  • the metal product is formed by depositing a metal such as a refractory metal in a molten salt bath by electrolysis on a portion of the surface of the conductive substrate exposed without forming a resist pattern.
  • examples of the metal product manufactured by the present invention include a contact probe, a micro connector, a micro relay, and various sensor parts.
  • examples of metal products manufactured by the present invention include RFMEMS (Radio Frequency Microscope) such as a variable capacitor, inductor, array, or antenna.
  • Electro Mechanical System optical MEMS members, inkjet heads, biosensor internal electrodes, or power MEMS members (electrodes, etc.).
  • the fluorine content in the molten salt bath of the present invention is too small, the effect of containing fluorine cannot be obtained. Since the tendency to scatter is increased, it is preferably 0.1 atomic% or more and 20 atomic% or less of the entire molten salt bath.
  • the fluorine content in the molten salt bath of the present invention was determined by dissolving the molten salt bath of the present invention in water. The sample can be detected and calculated by using a fluoride ion selective electrode.
  • the molten salt bath of the present invention is prepared by, for example, heating at least a mixture of zinc chloride, bromide or iodide, alkali metal chloride, bromide or iodide, and a fluorine compound. It can be obtained by melting.
  • the molten salt bath thus obtained is accommodated, for example, in an electrolytic cell 1 shown in the schematic configuration diagram of FIG. Then, after immersing anode 3 and cathode 4 in molten salt bath 2 accommodated in electrolytic cell 1, current is passed between anode 3 and cathode 4 to perform electrolysis of molten salt bath 2. For example, the metal contained in the molten salt bath 2 can be deposited on the surface of the cathode 4 to obtain a deposit.
  • the precipitate was precipitated in a state where 0.01 atomic% or more of oxygen was contained in the molten salt bath 2. In this case, a higher purity precipitate tends to be obtained.
  • oxygen is introduced into the molten salt bath 2.
  • preparation of a molten salt bath 2 in which an acid salt is mixed can be mentioned.
  • the oxygen content is a ratio (atomic%) when the total of all the components constituting the molten salt bath 2 containing oxygen is 100 atomic%. Further, the oxygen content in the molten salt bath 2 can be calculated using the above-described inert gas melting infrared absorption method.
  • the surface roughness of the surface of the precipitate is 3
  • surface roughness means arithmetic average roughness (Ra FIS B0601-1994).
  • the relative density of the precipitates is preferably 85% or more.
  • the relative density of the precipitate is less than 85%, the voids in the precipitate increase and the salt tends to be easily involved.
  • the residual stress in the precipitate increases, and the precipitate may peel off during the formation of the precipitate.
  • "relative density of precipitates” in the present invention the proportion of the original density of the metal intended to! /, Ru that precipitation density of the precipitate for (gZcm 3) (gZcm 3) of (%) It is expressed by the following formula.
  • Relative density of precipitates 100 X (density of precipitates) / (gold intended to precipitate) The original density of the genus)
  • Each powder of potassium was dried in a vacuum oven at 200 ° C. for 12 hours.
  • the WC1 (tungsten tetrachloride) powder was dried in a 100 ° C vacuum oven for 12 hours.
  • Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.
  • the molten salt bath of Example 1 was prepared in an amount of 500 g by heating the resulting alumina crucible to melt the powder in the alumina crucible.
  • Table 2 shows the composition (atomic%) of this molten salt bath.
  • the composition of the molten salt bath shown in Table 2 is as follows: ZnCl, NaCl contained in the alumina crucible
  • the evaluation of the composition of the precipitate is performed by ICP spectroscopic analysis after the precipitate is dissolved in an acid.
  • the amount of tungsten contained in the precipitate increases (the tungsten (shown in Table 3)).
  • the components other than W, Zn and O shown in Table 3 are mainly constituents of the molten salt bath, and are present in the voids of the precipitate.
  • the smaller the component amount (the smaller the atomic% in the other column of Table 3), the higher the density and the higher the amount of the precipitate.
  • the surface roughness of the precipitate was evaluated using a laser microscope (model number “VK-8 500” manufactured by Keyence Corporation). The lower the surface roughness value shown in Table 3, the more the precipitate has a smoother surface.
  • the surface roughness shown in Table 3 is the arithmetic average roughness Ra (JIS B0601-1994).
  • the density of precipitates was evaluated by using a FIB (focused ion beam) apparatus to cut the vicinity of the center of the precipitates into a 3 mm x 3 mm rectangular plate together with the nickel plate, This was done by calculating the density of the precipitate.
  • the density of the precipitate was calculated as follows. First, the thickness of the precipitate in the sample was measured using a FIB apparatus. Then, the volume of the precipitate was calculated by multiplying the surface area (3 mm ⁇ 3 mm) of the precipitate by the measured thickness. On the other hand, the mass of the portion corresponding to the cut nickel plate was calculated from the mass of the whole nickel plate measured in advance.
  • the mass of the entire sample was measured, and the mass of the precipitate was calculated by subtracting the mass of the portion corresponding to the cut nickel plate from the measured mass of the entire sample. Finally, the density of the precipitate was calculated by dividing the mass of the precipitate by the volume of the precipitate.
  • the relative density of the precipitate is assumed to be 19.3 (gZcm 3 ), which is the original density of tungsten, which is a metal intended to be precipitated. From the original density, the relative density (%) of the precipitate was calculated by the following formula.
  • Relative density of precipitates 100 X (precipitate density) Z (original density of tungsten) [0045] As shown in Table 3, the precipitate obtained using the molten salt bath of Example 1 is a film-like precipitate, has a large amount of tungsten, is highly pure, and has a small surface roughness. It was a high density, high relative density and high density precipitate.
  • the above glove box is adjusted so that KF force mol and WC1 are 0.54 mol per 00 mol.
  • Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.
  • the precipitate obtained using the molten salt bath of Example 2 was film-like, had a large amount of tungsten, had a high purity, and had a small surface roughness. It was a high density, high relative density and high density precipitate.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • the WC1 powder was dried in a 100 ° C vacuum oven for 12 hours. It was. A mixture of ZnCl, NaCl, and KC1 with a molar ratio of 85: 10: 5 was prepared.
  • Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.
  • Example 3 the alumina crucible was heated to melt the powder in the alumina crucible, whereby the molten salt bath of Example 3 was produced.
  • Table 2 shows the composition (atomic%) of this molten salt bath.
  • Example 3 by performing the electrolysis under the same electrolysis conditions as in Example 1 (Table 3) except that the molten salt bath of Example 3 was used and the temperature of the molten salt bath was maintained at 380 ° C, A precipitate containing tungsten was obtained on the surface of the nickel plate.
  • the precipitate obtained using the molten salt bath of Example 3 is a film-like precipitate, has a large amount of tungsten, is highly pure, and has a small surface roughness. It was a high density, high relative density and high density precipitate.
  • the compound is placed in an alumina crucible, and KF force mol, WC1 is 100 mol per 100 mol of this mixture.
  • Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.
  • Example 4 Thereafter, in the same manner as in Example 1, the molten salt bath of Example 4 was produced by heating the alumina crucible to melt the powder in the alumina crucible. Table 2 shows the composition (atomic%) of this molten salt bath.
  • Example 3 using the molten salt bath of Example 4, electrolysis was performed under the same electrolysis conditions as in Example 1 (Table 3) to obtain a precipitate containing tungsten on the surface of the nickel plate. . [0060] Thereafter, in the same manner as in Example 1, the precipitation state, composition, surface roughness, density and relative density of the precipitates were evaluated. The results are shown in Table 3.
  • the precipitate obtained by using the molten salt bath of Example 4 is in the form of a film, has a large amount of tungsten, is highly pure, and has a small surface roughness. It was a high density, high relative density and high density precipitate.
  • WC1 is 0.27 mol and WO is 0.27 mol.
  • Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.
  • Example 5 500 g of the molten salt bath of Example 5 was prepared by heating the alumina crucible containing 2 4 3 to melt the powder in the alumina crucible. It is shown the composition of the molten salt bath (atomic 0/0) in Table 2.
  • Example 5 using the molten salt bath of Example 5, electrolysis was performed under the same electrolysis conditions as in Example 1 (Table 3) to obtain a precipitate containing tungsten on the surface of the nickel plate. .
  • the precipitate obtained using the molten salt bath of Example 5 is a film-like precipitate, has a large amount of tungsten, is highly pure, and has a small surface roughness. It was a high density, high relative density and high density precipitate.
  • the composition (molar ratio) of the raw materials contained in the alumina crucible is shown in Table 1. [0070] And ZnBr, NaBr, KBr, KF and WC1 are contained in the above glove box.
  • Example 6 The molten alumina crucible obtained in Example 6 was heated to melt the powder in the alumina crucible, thereby preparing 500 g of the molten salt bath of Example 6.
  • Table 2 shows the composition (atomic%) of this molten salt bath.
  • Example 6 electrolysis was performed under the same electrolysis conditions as in Example 1 (Table 3) to obtain a precipitate containing tungsten on the surface of the nickel plate. .
  • the precipitate obtained using the molten salt bath of Example 6 was film-like, had a large amount of tungsten, had a high purity, and had a small surface roughness. It was a high density, high relative density and high density precipitate.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • the WC1 powder was dried in a 100 ° C vacuum oven for 12 hours.
  • Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible. Show.
  • Example 7 Thereafter, in the same manner as in Example 1, the molten salt bath of Example 7 was produced by heating the alumina crucible and melting the powder in the alumina crucible. Table 2 shows the composition (atomic%) of this molten salt bath.
  • Example 7 electrolysis was performed under the same electrolysis conditions as in Example 1 (Table 3), thereby obtaining a precipitate containing tungsten on the surface of the nickel plate. .
  • the precipitate obtained by using the molten salt bath of Example 7 is a film-like precipitate, has a large amount of tungsten, is highly pure, and has a small surface roughness. It was a high density, high relative density and high density precipitate.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • the WC1 powder was dried in a 100 ° C vacuum oven for 12 hours.
  • KF is 4 moles and WC1 is 0.54 moles.
  • Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.
  • Example 8 Thereafter, in the same manner as in Example 1, the alumina crucible was heated to melt the powder in the alumina crucible, whereby the molten salt bath of Example 8 was produced. Table 2 shows the composition (atomic%) of this molten salt bath.
  • the precipitate obtained using the molten salt bath of Example 8 was in the form of a film, had a large amount of tungsten, had a high purity, and had a small surface roughness. It was a high density, high relative density and high density precipitate.
  • Example 9 Weighing power of powder A precipitate containing tungsten on the surface of the nickel plate was obtained in the same manner as in Example 1 except that the steps up to obtaining a precipitate containing tungsten were performed in the atmosphere.
  • Table 1 shows the composition (molar ratio) of the raw materials accommodated in the alumina crucible in Example 9, and Table 2 shows the composition (atomic%) of the molten salt bath.
  • the oxygen content (atomic%) in the molten salt bath was calculated using an inert gas melting infrared absorption method for a sample obtained by extracting a part of the molten salt bath. The reason why the molten salt bath of Example 9 contains oxygen is thought to be due to the mixing of oxygen in the atmosphere.
  • the precipitate obtained using the molten salt bath of Example 9 had a film-like precipitation state, a large amount of tungsten, a high purity, and a small surface roughness. It was a high density, high relative density and high density precipitate.
  • Table 1 shows the composition (molar ratio) of the raw materials housed in the alumina crucible in Example 10. Then, an alumina tube was inserted into the molten salt bath in the alumina crucible, and oxygen was introduced at a flow rate of 1 LZ for publishing with oxygen for 1 hour or more. Thus the composition of the molten salt bath of Example 10 obtained (atomic 0/0) are shown in Table 2 ⁇ this.
  • the oxygen content (atomic%) in the molten salt bath was calculated using an inert gas melting infrared absorption method for a sample obtained by extracting a part of the molten salt bath. The reason why oxygen is contained in the molten salt bath of Example 10 is considered to be due to the mixing of oxygen in the atmosphere and the dissolution of oxygen introduced by the tube made by Armina.
  • the precipitate obtained using the molten salt bath of Example 10 had a precipitation state. It was a film-like precipitate with a high amount of tungsten, high purity, small surface roughness, high density, high relative density, and high density.
  • ZnCl and NaCl powders are dried in a vacuum oven at 200 ° C for 12 hours
  • Table 1 shows the composition (molar ratio) of the raw materials housed inside.
  • the molten salt bath of Comparative Example 1 was heated by melting the powder by heating the crucible.
  • Table 2 shows the composition (atomic%) of this molten salt bath.
  • the precipitates obtained using the molten salt bath of Comparative Example 1 were granular in the precipitation state, and the amount of tungsten compared to the precipitates of Example 1 to L0: It was a precipitate with a very small surface roughness and a small density, a low density and a low relative density.
  • Table 1 shows the composition (molar ratio) of the raw materials contained in the crucible.
  • Example 3 As shown in Table 3, the precipitate obtained using the molten salt bath of Comparative Example 2 is cracked, and the amount of tungsten is much higher than that of Example 1-: LO precipitate.
  • the precipitates had a small surface roughness, a large density, a low density, and a low relative density.
  • Example 1 60 20 0 0 0 0 0 4 0.54 0
  • Example 2 35 30 30 5 0 0 0 0 4 0.54 0
  • Example 3 85 10 5 0 0 0 0 0 4 0.54 0
  • Example 4 60 20 0 0 20 0 0 0 4 0.54 0 ⁇
  • Example 5 60 20 0 0 0 0 0 4 0.27 0.27
  • Example 6 0 0 0 0 0 60 20 4 0.50 0
  • Example 7 49
  • Example 7 70 15 15 0 0 0 0 0 4 0.54 0
  • Example 9 60 20 0 0 0 0 0 4 0.54 0
  • Example 10 60 20 0 0 0 0 0 0 0 0 0.54 0
  • Comparative Example 1 60 40 0 0 0 0 0 0 0 0 0.0 0.54 0
  • Example 10 60 20 0 0 0 0 0 0 0.54 0
  • Example 1 22.16 7.39 8.87 0 0 59.90 0 0.20 1.48 0
  • Example 2 14.25 12.21 13.84 2.03 0 55.82 0 0.22 1.63 0
  • Example 3 28.75 3.38 3.04 0 0 63.30 0 0.18 1.35 0
  • Example 4 22.16 7.39 1.48 0 7.39 59.90 0 0.20 1.48 0
  • Example 5 22.19 7.40 8.87 0 0 59.56 0 0.20 1.48 0.30
  • Example 6 22.18 7.39 8.87 0 0 0.74 59.15 0.19 1.48 0
  • Example 7 18.83 11.53 9.61 0 0 58.28 0 0.21 1.54 0
  • Example 8 24.94 5.34 6.77 0 0 61.33 0 0.19 1.43 0
  • Example 9 22.14 7.38 8.86 0 0 59.84 0 0.20 1.48 0.10
  • Example 10 22.10 7.37 8.84 0 0
  • Examples 1 to 5 containing fluorine When using a molten salt bath of LO V, in the case of containing no fluorine, the molten salt bath of Comparative Example 12 Compared with the case of using, it was possible to obtain a precipitate with a high purity, high relative density and high density, and a smooth surface. [0107] Further, as shown in Tables 2 and 3, the melting of Example 1 and Examples 4 to 10 in which the zinc content in the entire molten salt bath is 17 atomic percent or more and 25 atomic percent or less. When using a salt bath, the temperature of the molten salt bath is 250 ° C compared to the case of using the molten salt baths of Examples 2 to 3, and precipitates can be obtained at a lower temperature. It was.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • Table 4 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.
  • the molten alumina crucible was heated to melt the powder in the alumina crucible, thereby preparing 500 g of the molten salt bath of Example 11.
  • Table 5 shows the composition (atomic%) of this molten salt bath.
  • the precipitation state, composition, surface roughness and density of the precipitates were evaluated in the same manner as in Example 1.
  • the relative density of the precipitate is assumed to be 10.22 (g / cm 3 ) of the original density of molybdenum, which is the metal intended to be deposited, and the calculated density of the precipitate and the original density of this molybdenum The relative density of the precipitate (%) was calculated.
  • Relative density of precipitates 100 X (density of precipitates) Z (original density of molybdenum) [0113]
  • the precipitates obtained using the molten salt bath of Example 11 Thiickness 3 m was a high-density, high-relative-density and high-density precipitate with a film-like precipitation state, high molybdenum content, high purity, and small surface roughness.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • Table 4 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.
  • the molten alumina crucible was heated to melt the powder in the alumina crucible, whereby 500 g of the molten salt bath of Example 12 was prepared.
  • Table 5 shows the composition (atomic%) of this molten salt bath.
  • Example 12 Thereafter, the precipitation state, composition, surface roughness, density and relative density of the precipitates were evaluated in the same manner as in Example 11. The results are shown in Table 6. [0119] As shown in Table 6, the precipitate (thickness 0.5 / zm) obtained using the molten salt bath of Example 12 was in the form of a film and had a large amount of molybdenum and a high content. It was a high density, high relative density and high density precipitate with low purity and surface roughness.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • the WO powder is dried in a vacuum oven at 100 ° C for 12 hours.
  • Table 4 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.
  • the molten salt crucible of Example 13 was prepared in an amount of 500 g by heating the resulting alumina crucible to melt the powder in the alumina crucible.
  • Table 5 shows the composition (atomic%) of this molten salt bath.
  • the precipitates (thickness 0.5 / zm) obtained using the molten salt bath of Example 13 were in the form of a film with a large amount of tungsten and a high amount.
  • the precipitates were pure, small in surface roughness, high density, high relative density and high density.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • Example 14 500 g of the molten salt bath of Example 14 was prepared by heating the alumina crucible that had been heated and melting the powder in the alumina crucible. Table 5 shows the composition (atomic%) of this molten salt bath.
  • the precipitation state, composition, surface roughness and density of the precipitates were evaluated in the same manner as in Example 1.
  • the relative density of the precipitate is assumed to be 16.65 (gZcm 3 ), which is the original density of tantalum, which is the metal intended to be deposited, and the calculated density of the tantalum and the original density of this tantalum. From the above, the relative density (%) of the precipitate was calculated by the following formula.
  • Relative density of precipitates 100 X (Precipitate density) Z (Original density of tantalum)
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • KF powder was weighed in the above glove box so as to be 4 mol. Then, the weighed KF powder was placed in the above-mentioned alumina crucible.
  • the lumina crucible was heated to melt the powder in the alumina crucible. Thereafter, 0.54 moles per 100 moles of the mixture of ZnCl, NaCl, and KC1 contained in the above alumina crucible
  • TiCl is weighed in the above glove box, and the weighed TiCl is
  • Example 15 500 g of the molten salt bath of Example 15 was prepared by adding it to the mina crucible.
  • Table 4 shows the composition (molar ratio) of the raw materials used to make this molten salt bath, and
  • Table 5 shows the composition (atomic%) of the molten salt bath.
  • a mirror-polished nickel plate having an arithmetic average roughness Ra of less than lOnm as a cathode, a tungsten rod having a diameter of 5 mm as an anode, and a zinc rod having a diameter of 5 mm as a reference electrode was immersed in the molten salt bath of Example 15.
  • the potential between the cathode and the anode is set to 60 mV by the three-electrode method that controls the potential of the nickel plate as the cathode.
  • electrolysis in (Table 6) By performing electrolysis in (Table 6), a precipitate containing titanium was obtained on the surface of the nickel plate as the cathode.
  • the precipitation state, composition, surface roughness and density of the precipitates were evaluated in the same manner as in Example 1.
  • the relative density of the precipitate was set to 4.54 (g / cm 3 ) as the original density of titanium, which is a metal intended to be deposited, and the density of the precipitate calculated above and Calculate the relative density (%) of the precipitate from the original density using the following formula. It was.
  • the precipitate (thickness 0.1 ⁇ m) obtained using the molten salt bath of Example 15 was in the form of a film with a large amount of titanium and a high amount of titanium. It was a high density, high relative density and high density precipitate with low purity and surface roughness.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • KF powder was weighed in the above glove box so as to be 4 mol. Then, the weighed KF powder was placed in the above-mentioned alumina crucible.
  • the lumina crucible was heated to melt the powder in the alumina crucible. After that, it becomes 1.1 mol with respect to 100 mol of the mixture of ZnCl, NaCl, and KC1 contained in the above-mentioned alumina crucible.
  • TiCl is weighed in the above glove box and the weighed TiCl is
  • Table 4 shows the composition (molar ratio) of the raw materials used to make this molten salt bath
  • Table 5 shows the composition (atomic%) of the molten salt bath.
  • a mirror-polished nickel plate having an arithmetic average roughness Ra of less than lOnm as a cathode, a tungsten rod having a diameter of 5 mm as an anode, and a zinc rod having a diameter of 5 mm as a reference electrode was immersed in the molten salt bath of Example 16.
  • the potential between the cathode and the anode is set to 60 mV by the three-electrode method that controls the potential of the nickel plate as the cathode.
  • the precipitate (thickness 0.1 ⁇ m) obtained using the molten salt bath of Example 16 was film-like, with a large amount of titanium and a high amount of titanium. It was a high density, high relative density and high density precipitate with low purity and surface roughness.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • KF powder was weighed in the above glove box so as to be 4 mol. Then, the weighed KF powder was placed in the above-mentioned alumina crucible.
  • the lumina crucible was heated to melt the powder in the alumina crucible. After that, it becomes 2.5 mol with respect to 100 mol of the mixture of ZnCl, NaCl, and KC1 contained in the above-mentioned alumina crucible.
  • TiCl is weighed in the above glove box and the weighed TiCl is
  • Table 4 shows the composition (molar ratio) of the raw materials used to make this molten salt bath
  • Table 5 shows the composition (atomic%) of the molten salt bath.
  • the precipitate (thickness 0.5 / zm) obtained using the molten salt bath of Example 17 was in the form of a film and had a large amount of titanium and a high content. It was a high density, high relative density and high density precipitate with low purity and surface roughness.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • Table 4 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.
  • the molten alumina crucible was heated to melt the powder in the alumina crucible, whereby 500 g of the molten salt bath of Example 18 was produced.
  • Table 5 shows the composition (atomic%) of this molten salt bath.
  • the precipitation state, composition, surface roughness and density of the precipitates were evaluated in the same manner as in Example 1.
  • the relative density of the precipitate is assumed to be 8.57 (g / cm 3 ) of the original density of niobium, which is the metal intended to be deposited, and the density of the precipitate calculated above and the density of this niobium Calculate the relative density (%) of the precipitate from the original density using the following formula. It was.
  • the precipitate (thickness 0.5 / zm) obtained using the molten salt bath of Example 18 was in the form of a film with a large amount of niobium and a high amount. It was a high density, high relative density and high density precipitate with a small surface roughness.
  • Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.
  • KF is 4 mol and VC1 (vanadium dichloride) is 0.54 mol.
  • Example 19 500 g of the molten salt bath of Example 19 was prepared by heating the alumina crucible thus melted to melt the powder in the alumina crucible. Table 5 shows the composition (atomic%) of this molten salt bath.
  • the precipitation state is the film form of Example 13, the amount of vanadium is high purity, the surface roughness is small,
  • Example 11 22.21 7.40 8.88 59.82 0 1.48 0 0.20 0 0 0 0 0
  • Example 12 22.12 7.37 8.85 59.98 0 1.47 0 0.20 0 0 0 0
  • Example 13 22.21 7.40 8.88 59.22 0.60 1.48 0.20 0 0 0 0 0
  • Example 14 22.08 7.36 8.83 58.87 0.99 1.47 0 0 0.40 0 0 0
  • Example 15 22.16 7.39 8.87 59.90 0 1.48 0 0 0 0.20 0 0
  • Example 16 21.95 7.32 8.78 60.10 0 1.46 0 0 0 0.40 0 0
  • Example 17 20.80 6.93 9.71 58.93 0 2.77 0 0 0 0.87 0 0
  • Example 18 22.12 7.37 8.85 59.98 0 1.47 0 0 0 0.20 0
  • Example 19 22.25 7.42
  • composition (Atom) Surface Relative Potential Time Precipitation Density
  • Example 11 250 150 3 Film-like 0 99 0 0 0 0 0 0 0.5 0.5 2.6 9.8 95.9
  • Example 12 250 150 3 Film-like 0 98 0 0 0 0 0 0.7 0.3 1.5 10.1 98.8
  • Example 13 250 60 3 Film-like 99 0 0 0 0 0 0 0.7 0.3 0.1 18.8 97.4
  • Example 14 250 60 3 Film type 0 0 99.1 0 0 0 0 0 0.1 0.8 1.9 15.1 90.7
  • Example 15 250 60 6 Film type 0 0 0 99 0 0 0 0 0 0.2 0.8 0.8 4.1 90 -3
  • Example 16 250 60 3 Film 0 0 0 99.1 0 0 0 0.2 0.7 1.4 4.2 92.5
  • Example 1 250 60 8 Film 0 0 0 0 98.9 0 0 0 0.3 0.8 2.3 4.1 90.3
  • Example 18 250 60 3 Film
  • a titanium layer was formed on the surface of a disk-shaped silicon substrate having a diameter of 3 inches by sputtering titanium with a thickness of 0.3 ⁇ m. Then, a photoresist having a width of 1 cm X, a length of 1 cm, and a thickness of 30 / zm made of PMMA was applied onto the titanium layer. Next, a portion of this photoresist is irradiated with SR light (synchrotron radiation), and the photoresist of the portion irradiated with SR light is selectively removed, so that the line Z space is 50 mZ5 on the titanium layer. A 0 ⁇ m striped resist pattern was formed.
  • SR light synchrotron radiation
  • the silicon substrate after the resist pattern was formed as a cathode, the tungsten rod as an anode, and these electrodes were melted with the same composition as the molten salt bath of Example 6. It was immersed in a salt bath lOOOOg. By then the titanium layer lcm 2 per 3mA current on the silicon substrate (current density 3mAZcm 2) by passing 60 hours perform constant current electrolysis between the electrodes while holding the molten salt bath 250 ° C, A precipitate containing tungsten was obtained on the titanium layer.
  • the silicon substrate was taken out with a glove box force.
  • the silicon substrate was washed with water to remove salt adhering to the silicon substrate.
  • a plasma using a mixed gas of CF (carbon tetrafluoride) and O (oxygen) is used.
  • the photoresist on the titanium layer was removed by mating. Finally, the precipitate on the titanium layer was mechanically peeled off to obtain a high-density and high-density electrode having a high tungsten purity and a smooth surface.
  • the molten salt bath of the present invention contains at least one selected from the group force consisting of chlorine, bromine and iodine, zinc, at least two alkali metals, and fluorine.
  • a precipitate having a high purity, high density and high density and a smooth surface can be obtained.

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Abstract

La présente invention a pour objet un bain de sel fondu (2) qui comprend au moins un élément sélectionné dans le groupe constitué par le chlore, le brome et l'iode, ainsi que du zinc, au moins deux métaux alcalins et du fluor. Ledit bain (2) peut également contenir de l’oxygène. Ledit bain (2) peut également contenir au moins un élément sélectionné au sein du groupe constitué par le tungstène, le chrome, le molybdène, le tantale, le titane, le zirconium, le vanadium, le hafnium et le niobium. La présente invention décrit également un précipité obtenu en employant ledit bain de sel fondu (2), une méthode d'obtention d'un composé métallique employant ledit bain (2), ainsi qu'un composé métallique obtenu par ladite méthode.
PCT/JP2005/017510 2004-10-01 2005-09-22 Bain de sel fondu, précipité obtenu en employant le bain de sel fondu, méthode d’obtention d’un composé métallique et composé métallique WO2006038476A1 (fr)

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US11/664,095 US20080105553A1 (en) 2004-10-01 2005-09-22 Molten Salt Bath, Deposit Obtained Using The Molten Salt Bath, Method Of Manufacturing Metal Product, And Metal Product
DE112005002435.0T DE112005002435B4 (de) 2004-10-01 2005-09-22 Salzschmelzebad, Abscheidung erhalten unter Verwendung des Salzschmelzebades, Herstellungsverfahren für ein Metallprodukt und Metallprodukt
CN2005800335362A CN101035930B (zh) 2004-10-01 2005-09-22 熔融盐浴、利用该熔融盐浴获得的析出物、金属制品制造方法及金属制品
JP2006539225A JP4785141B2 (ja) 2004-10-01 2005-09-22 溶融塩浴、この溶融塩浴を用いて得られた析出物、金属製品の製造方法および金属製品

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JP2010201390A (ja) * 2009-03-05 2010-09-16 Sumitomo Electric Ind Ltd 光触媒素子
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WO2011102059A1 (fr) * 2010-02-19 2011-08-25 住友電気工業株式会社 Structure de stratifié métallique et procédé de production de celle-ci
JP2015193899A (ja) * 2013-11-19 2015-11-05 住友電気工業株式会社 電析用電解質および金属膜の製造方法
US9199433B2 (en) 2009-06-30 2015-12-01 Sumitomo Electric Industries, Ltd. Metal laminated structure and method for producing the metal laminated structure
WO2019171744A1 (fr) * 2018-03-08 2019-09-12 住友電気工業株式会社 Élément plaqué au titane, et procédé de fabrication de celui-ci
JPWO2018216319A1 (ja) * 2017-05-22 2020-03-19 住友電気工業株式会社 チタンめっき部材の製造方法
WO2021176769A1 (fr) * 2020-03-04 2021-09-10 住友電気工業株式会社 Électrolyte pour placage de titane et procédé de production d'élément plaqué au titane utilisant l'électrolyte pour le placage de titane

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JP2010201390A (ja) * 2009-03-05 2010-09-16 Sumitomo Electric Ind Ltd 光触媒素子
US20100243456A1 (en) * 2009-03-27 2010-09-30 Sumitomo Electric Industries, Ltd. Molten salt bath, method for preparing the same, and tungsten film
JP2010229518A (ja) * 2009-03-27 2010-10-14 Sumitomo Electric Ind Ltd 溶融塩浴、溶融塩浴の製造方法およびタングステン膜
US9199433B2 (en) 2009-06-30 2015-12-01 Sumitomo Electric Industries, Ltd. Metal laminated structure and method for producing the metal laminated structure
US8993121B2 (en) 2010-02-19 2015-03-31 Sumitomo Electric Industries, Ltd. Metal laminated structure and method for producing the same
JP2011171564A (ja) * 2010-02-19 2011-09-01 Sumitomo Electric Ind Ltd 金属積層構造体および金属積層構造体の製造方法
WO2011102059A1 (fr) * 2010-02-19 2011-08-25 住友電気工業株式会社 Structure de stratifié métallique et procédé de production de celle-ci
JP2015193899A (ja) * 2013-11-19 2015-11-05 住友電気工業株式会社 電析用電解質および金属膜の製造方法
JPWO2018216319A1 (ja) * 2017-05-22 2020-03-19 住友電気工業株式会社 チタンめっき部材の製造方法
WO2019171744A1 (fr) * 2018-03-08 2019-09-12 住友電気工業株式会社 Élément plaqué au titane, et procédé de fabrication de celui-ci
JPWO2019171744A1 (ja) * 2018-03-08 2021-03-11 住友電気工業株式会社 チタンめっき部材の製造方法及びチタンめっき部材
JP7086172B2 (ja) 2018-03-08 2022-06-17 住友電気工業株式会社 チタンめっき部材の製造方法及びチタンめっき部材
WO2021176769A1 (fr) * 2020-03-04 2021-09-10 住友電気工業株式会社 Électrolyte pour placage de titane et procédé de production d'élément plaqué au titane utilisant l'électrolyte pour le placage de titane

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