WO2006038476A1 - Fused-salt bath, precipitate obtained by using the fused-salt bath, method for producing metal product and metal product - Google Patents

Abstract

A fused-salt bath (2) which comprises at least one selected from the group consisting of chlorine, bromine and iodine, zinc, at lest two alkali metals and fluorine. The fused-salt bath (2) may further comprise oxygen. The fused-salt bath (2) may further comprise at least one selected from the group consisting of tungsten, chromium, molybdenum, tantalum, titanium, zirconium, vanadium, hafnium and niobium. A precipitate prepared by using the above fused-salt bath (2), a method for producing a metal product, which uses the above fused-salt bath (2), and a metal product produced by the method are also provided.

Description

 Specification

 Molten salt bath, precipitate obtained using the molten salt bath, method for producing metal product, and metal product

 Technical field

 [0001] 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.

 Background art

 Conventionally, a technique for depositing a metal from a bath by electrolysis has been used in the production of a metal product or coating of a base material by electrolysis. In particular, in recent years, MEMS (Micro Electro Mechanical Systems), which enables the production of small metal products that are compact, highly functional, and energy-saving, are attracting attention in various fields such as telecommunications, medicine, neurology, and automobiles. Therefore, it is conceivable to manufacture a fine metal product applied to MEMS using a technique for depositing a metal by electrolysis or to coat the surface of a fine metal product.

 [0003] On the other hand, 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

ELECTROCHEMISTRY 21 (1991), p. 158— 165

 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

 Disclosure of the invention

 Problems to be solved by the invention

[0004] However, force such as nickel and copper can be deposited by electrolysis after dissolving in water. Refractory metal is deposited by electrolysis using an aqueous solution. There was a problem that could not be done.

[0005] Thus, for example, zinc salt or bromide and sodium salt or bromide

The force that is used to deposit refractory monometals by electrolysis using a molten salt bath in which a refractory metal compound is melted is low in purity, density, and compactness. Coarse, become things! /

[0006] 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. To provide a product, a method for manufacturing a metal product, and a metal product.

 Means for solving the problem

[0007] 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.

Here, the molten salt bath of the present invention may contain oxygen.

 Further, the molten salt bath of the present invention has a group force of tungsten, chromium, molybdenum, tantalum, titanium, zirconium, vanadium, hafnium, and niobium force.

May contain one species.

 [0009] 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.

[0010] In addition, for the molten salt bath of the present invention, it is preferable that the zinc content is 14 atomic% or more and 30 atomic% or less of the entire molten salt bath. [0011] Further, in the molten salt bath of the present invention, it is preferable that the zinc content is 17 atomic% or more and 25 atomic% or less of the entire molten salt bath.

[0012] Further, in the molten salt bath of the present invention, the fluorine content is 0.1 atom of the entire molten salt bath.

It is preferable to be at least 20% by atom.

[0013] Further, the present invention is a precipitate obtained using the molten salt bath described above. Here, 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.

[0014] Further, 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.

[0015] The relative density of the precipitate of the present invention is preferably 85% or more.

 Furthermore, 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. Here, in the method for producing a metal product of the present invention, the temperature of the molten salt bath may be 250 ° C. or less.

[0016] Further, the present invention is a metal product manufactured by using the above metal product manufacturing method.

 The invention's effect

 [0017] According to the present invention, 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.

 Brief Description of Drawings

 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.

 Explanation of symbols

 [0019] 1 electrolytic cell, 2 molten salt bath, 3 anode, 4 cathode.

BEST MODE FOR CARRYING OUT THE INVENTION [0020] 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. Here, 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. For example, these components may exist as ions in the molten salt bath, or may exist in a complexed state. Further, 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.

 [0021] The molten salt bath of the present invention may contain oxygen in addition to the above components. 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. Further, 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.

 [0022] 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. Here, 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.

[0023] 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. In addition, the form of 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

[0024] In addition, 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. In addition, 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. Therefore, when 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.

 [0025] 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.

[0026] In addition, 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. Here, except 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. Preferably not present in the molten salt bath.

 [0027] Further, it is preferable that 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. Even when an electric mold in which a resist pattern made of a resin such as metatalylate (PMMA) is formed is immersed, deformation of the resist pattern due to the temperature of the molten salt bath can be suppressed. Therefore, in this case, 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.

 Here, as 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. Further, 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. Further, examples of the metal product manufactured by the present invention include a contact probe, a micro connector, a micro relay, and various sensor parts. In addition, 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.).

[0029] If 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.

 [0030] 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.

 [0031] 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.

 [0032] Here, it is preferable that 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. As a technique for containing oxygen in the molten salt bath 2, for example, in addition to performing the steps from the preparation of the molten salt bath 2 to obtaining the precipitate in the atmosphere, oxygen is introduced into the molten salt bath 2. In addition, 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.

 [0033] From the viewpoint of obtaining a precipitate having a smooth surface, the surface roughness of the surface of the precipitate is 3

 m or less is preferable. Here, in the present invention, “surface roughness” means arithmetic average roughness (Ra FIS B0601-1994).

[0034] The relative density of the precipitates is preferably 85% or more. When the relative density of the precipitate is less than 85%, the voids in the precipitate increase and the salt tends to be easily involved. In addition, the residual stress in the precipitate increases, and the precipitate may peel off during the formation of the precipitate. Here, "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)

 Example

 [0035] (Example 1)

 ZnCl (salt 匕 zinc), NaCl (salt 匕 sodium), KC1 (salt 匕 potassium) and KF (Futsui 匕)

2

 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.

Four

 . Then, when the molar ratio of ZnCl, NaCl, and KCl is 60:20:20, Ar (argon) atmosphere is used.

 2

 After these powders were weighed in a glove box under the atmosphere, these powders were accommodated in an alumina crucible in the same glove box.

 [0036] In addition, a mixture of ZnCl, NaCl, and KC1 contained in the above-mentioned alumina crucible 100 mol

 2

 Against the above glove box, KF force mol, WC1 is 0.54 mol

 Four

 After weighing each of KF and WC1 powders, these were put in the above-mentioned alumina crucible.

 Four

 The powder was contained. Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.

[0037] And ZnCl, NaCl, KC1, KF and WC1 are accommodated in the above glove box.

 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

 2

, Calculated from the composition of KC1, KF and WC1.

 Four

[0038] Then, in the above glove box, a mirror-polished nickel plate with an arithmetic average roughness Ra (jIS B0601-1994) of less than lOnm was used as the cathode, and a 5 mm diameter tungsten bar as the anode. It was immersed in the molten salt bath of Example 1. Then, while maintaining the temperature of the molten salt bath 250 ° C, a current was passed for 10 hours between said electrodes to nickel plate lcm ² per 3mA current (current density 3mAZcm 2) flows. By conducting the electrolysis under such electrolysis conditions (Table 3), a precipitate containing tungsten was obtained on the surface of the nickel plate as the cathode.

[0039] Thereafter, a nickel plate having a precipitate containing tungsten was taken out into the atmosphere from the glove box, and the precipitation state, composition, surface roughness and density of the precipitate were evaluated. The results are shown in Table 3. [0040] It should be noted that the precipitation state of the precipitates was evaluated by determining whether or not the precipitates were in the form of a film in close contact with the nickel plate by observation using a SEM (scanning electron microscope). In this observation, when the film was formed, the electrodeposition was evaluated as good, and when the precipitate was precipitated in the form of particles or cracked, the electrodeposition was evaluated as poor electrodeposition.

 [0041] The evaluation of the composition of the precipitate is performed by ICP spectroscopic analysis after the precipitate is dissolved in an acid. As the amount of tungsten contained in the precipitate increases (the tungsten (shown in Table 3)). The higher the atomic% of W), the higher the purity. In addition, the components other than W, Zn and O shown in Table 3 (other columns 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.

 Further, 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).

 [0043] In addition, 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. Then, 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.

[0044] Further, 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.

 [Example 2]

 ZnCl, NaCl, KC1, LiCl (lithium chloride) and KF powders at 200 ° C

2

 Dry in a vacuum oven for 12 hours. Also, WC1 powder is vacuum oven at 100 ° C

 Four

 Dried in for 12 hours. And ZnCl, NaCl, KCl and LiCl in molar ratio 35: 30: 3

 2

 These powders were weighed in a glove box under an Ar atmosphere so as to be 0: 5, and then stored in an alumina crucible in the same glove box.

[0047] In addition, a mixture of ZnCl, NaCl, KC1, and LiCl contained in the above-described alumina crucible 1

 2

 The above glove box is adjusted so that KF force mol and WC1 are 0.54 mol per 00 mol.

 Four

 Each of these powders was weighed in a tassel, and then these powders were accommodated in the above-mentioned alumina crucible. Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.

[0048] In the above glove box, ZnCl, NaCl, KC1, LiCl, KF and WC1

 2 4 By heating the contained alumina crucible to melt the powder in the alumina crucible

Then, 500 g of the molten salt bath of Example 2 was prepared. Shows the composition of the molten salt bath (atomic _^0/0) in Table 2

[0049] The same electrolysis conditions as in Example 1 except that the temperature of the molten salt bath was maintained at 430 ° C.

 By performing the electrolysis in (Table 3), a precipitate containing tungsten on the surface of the nickel plate was obtained.

 [0050] Thereafter, evaluation was performed on the precipitation state, composition, surface roughness, density and relative density of the precipitates in the same manner as in Example 1. The results are shown in Table 3.

 [0051] As shown in Table 3, 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.

 [0052] (Example 3)

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

Let dry for hours. 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.

 2

 The above-mentioned gloss is adjusted so that KF force mol and WC1 are 0.54 mol per 100 mol of the mixture.

 Four

 Each of these powders was weighed in a tube box, and then these powders were accommodated in the alumina crucible. Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.

 [0053] Then, 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 3 was produced. Table 2 shows the composition (atomic%) of this molten salt bath.

 [0054] Then, 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.

[0055] Thereafter, evaluation was performed in the same manner as in Example 1 on the precipitation state, composition, surface roughness, density, and relative density of the precipitates. The results are shown in Table 3.

[0056] As shown in Table 3, 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.

[Example 4]

 ZnCl, NaCl, CsCl (cesium chloride) and KF powder at 200 ° C vacuum

2

 Dry in oven for 12 hours. Also, the powder of WC1 is in a 100 ° C vacuum oven.

 Four

 Dry for 12 hours. Then, the molar ratio of ZnCl, NaCl and CsCl was 60:20:20.

 2

 The compound is placed in an alumina crucible, and KF force mol, WC1 is 100 mol per 100 mol of this mixture.

 Four

This was placed in the above-mentioned alumina crucible so as to be 0.5 mol. Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.

[0058] 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.

[0059] And, 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.

 [0061] As 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.

 [Example 5]

 20 powders of ZnCl, NaCl, KC1, KF and WO (tungsten trioxide)

twenty three

 Dry in a vacuum oven at 0 ° C for 12 hours. In addition, the powder of WC1 is vacuumed at 100 ° C.

 Four

 Dry in oven for 12 hours. And ZnCl, NaCl and KCl in molar ratio 60: 20: 2

 2

 These powders were weighed in a glove box under an Ar atmosphere so as to be 0, and then stored in an alumina crucible in the same glove box.

[0063] Further, a mixture of ZnCl, NaCl, and KC1 contained in the above-mentioned alumina crucible 100 mol

 2

 Against KF force mol, WC1 is 0.27 mol and WO is 0.27 mol.

 4 3

 After weighing KF, WC1 and WO powders in the glove box,

 4 3

 These powders were accommodated in the above-mentioned alumina crucible. Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.

[0064] In the above glove box, ZnCl, NaCl, KC1, KF, WC1 and WO

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.

 [0065] And, 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. .

[0066] Thereafter, evaluation was performed in the same manner as in Example 1 on the precipitation state, composition, surface roughness, density, and relative density of the precipitates. The results are shown in Table 3.

[0067] As shown in Table 3, 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.

[Example 6] That of ZnBr (zinc bromide), NaBr (sodium bromide), KBr (potassium bromide) and KF

2

 Each powder was dried in a 200 ° C. vacuum oven for 12 hours. Also, WC1 powder 1

 Four

 Dry in a vacuum oven at 00 ° C for 12 hours. ZnBr, NaBr and KBr

 2

 These powders were weighed in a glove box under an Ar atmosphere so that the ratio was 60:20:20, and then these powders were accommodated in an alumina crucible in the same glove box.

 [0069] In addition, a mixture of ZnBr, NaBr, and KBr contained in the alumina crucible described above

 2

 In the above glove box, KF force mol and WC1 are 0.5 mol against

 Four

 After weighing each of the KF and WC1 powders in the above, they are placed in the above-mentioned alumina crucible.

 Four

 Of powder. 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.

 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.

[0071] And, using the molten salt bath of 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. .

[0072] Thereafter, evaluation was performed on the precipitation state, composition, surface roughness, density and relative density of the precipitates in the same manner as in Example 1. The results are shown in Table 3.

[0073] As shown in Table 3, 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.

[Example 7]

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. The WC1 powder was dried in a 100 ° C vacuum oven for 12 hours.

 Four

 It was. A mixture of ZnCl, NaCl and KC1 with a molar ratio of 49:30:21 was prepared.

 2

 The above gloss is adjusted so that KF is 4 mol and WC1 is 0.54 mol for 100 mol of the mixture.

 Four

Each of these powders was weighed in a tube box, and then these powders were accommodated in the alumina crucible. Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible. Show.

 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.

 [0076] Then, using the molten salt bath of 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. .

[0077] Thereafter, evaluation was performed on the precipitation state, composition, surface roughness, density and relative density of the precipitates in the same manner as in Example 1. The results are shown in Table 3.

[0078] As shown in Table 3, 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.

[0079] (Example 8)

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. The WC1 powder was dried in a 100 ° C vacuum oven for 12 hours.

 Four

 It was. A mixture of ZnCl, NaCl and KC1 with a molar ratio of 70:15:15 was prepared.

 2

 For 100 moles, KF is 4 moles and WC1 is 0.54 moles.

 Four

 These powders were weighed in a box, and then stored in the alumina crucible. Table 1 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.

[0080] 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.

 [0081] Then, by performing electrolysis under the same electrolysis conditions as in Example 1 (Table 3) using the molten salt bath of Example 8, a precipitate containing tungsten on the surface of the nickel plate was obtained. .

[0082] 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.

[0083] As shown in Table 3, 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. Here, 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.

 [0085] Thereafter, evaluation was performed on the precipitation state, composition, surface roughness, density, and relative density of the precipitate in the same manner as in Example 1. The results are shown in Table 3.

 [0086] As shown in Table 3, 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.

 [Example 10]

Powder weighing power All processes up to melting of powder in an alumina crucible were carried out in the air. Here, 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. Here, 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.

 [0088] Thereafter, electrolysis was carried out under the same electrolysis conditions as in Example 1 (Table 3), thereby depositing a precipitate containing tungsten on the surface of the nickel plate.

 [0089] Thereafter, evaluation was performed on the precipitation state, composition, surface roughness, density, and relative density of the precipitates in the same manner as in Example 1. The results are shown in Table 3.

[0090] As shown in Table 3, 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.

 [0091] (Comparative Example 1)

 ZnCl and NaCl powders are dried in a vacuum oven at 200 ° C for 12 hours

2

 Let The powder of WC1 was dried in a vacuum oven at 100 ° C for 12 hours. And

 Four

 In a glove box under an Ar atmosphere so that the molar ratio of ZnCl and NaCl is 60:40

2

 Each of these powders was weighed and then stored in an alumina crucible in the same glove box.

[0092] Further, with respect to 100 moles of the mixture of ZnCl and NaCl contained in the above-mentioned alumina crucible

 2

 WC1 powder in the above glove box so that WC1 is 0.54 mol.

4 4

 After weighing each, WC1 powder was placed in the alumina crucible. Alumina crucible

 Four

 Table 1 shows the composition (molar ratio) of the raw materials housed inside.

[0093] Then, aluminum containing ZnCl, NaCl and WC1 in the above glove box

 twenty four

 The molten salt bath of Comparative Example 1 was heated by melting the powder by heating the crucible.

Og was produced. Table 2 shows the composition (atomic%) of this molten salt bath.

[0094] Then, by using the molten salt bath of Comparative Example 1 and setting the temperature of the molten salt bath to 400 ° C, electrolysis was performed under the same electrolysis conditions as in Example 1 (Table 3). A precipitate containing tungsten was obtained on the surface of the plate.

[0095] Thereafter, evaluation was performed in the same manner as in Example 1 on the precipitation state, composition, surface roughness, density, and relative density of the precipitates. The results are shown in Table 3.

[0096] As shown in Table 3, 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.

[0097] (Comparative Example 2)

 Each powder of ZnCl, NaCl and KC1 in a vacuum oven at 200 ° C for 12 hours

2

 Dried. The powder of WC1 was dried in a vacuum oven at 100 ° C for 12 hours. So

 Four

 In order to obtain a molar ratio of 60:20:20 for ZnCl, NaCl, and KC1,

 2

Weigh each of these powders in the microwave box and place them in the same glove box. These powders were placed in an alumina crucible.

 [0098] Further, a mixture of ZnCl, NaCl, and KC1 contained in the above-mentioned alumina crucible 100 mol

 2

 WC1 powder in the above glove box so that WC1 is 0.54 mol.

 After weighing 4 4, WC1 powder was placed in the alumina crucible. Aluminum

 Four

 Table 1 shows the composition (molar ratio) of the raw materials contained in the crucible.

[0099] Then, ZnCl, NaCl, KC1 and WC1 were accommodated in the glove box.

 twenty four

 By heating the alumina crucible and melting these powders, 500 g of the molten salt bath of Comparative Example 2 was produced. Table 2 shows the composition (atomic%) of this molten salt bath.

[0100] Then, using the molten salt bath of Comparative Example 2, 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.

[0101] Thereafter, evaluation was performed in the same manner as in Example 1 on the precipitation state, composition, surface roughness, density, and relative density of the precipitates. The results are shown in Table 3.

[0102] 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.

[0103] [Table 1]

Composition of raw materials (molar ratio)

ZnCI ₂ NaCI KCI LiCI CsCI ZnBr ₂ NaBr KBr KF WCI ₄ 0 ₃ Example 1 60 20 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 20 0 0 0 0 0 4 0.27 0.27 Example 6 0 0 0 0 0 60 20 20 4 0.50 0 Example 7 49 30 21 0 0 0 0 0 4 0- 54 0 Example 8 70 15 15 0 0 0 0 0 4 0.54 0 Example 9 60 20 20 0 0 0 0 0 4 0.54 0 Example 10 60 20 20 0 0 0 0 0 4 0.54 0 Comparative Example 1 60 40 0 0 0 0 0 0 0 0.54 0 Comparative Example 2 60 20 20 0 0 0 0 0 0 0.54 0

Ii formation of molten salt bath (atomic <½)

Ζη Na KU Cs CI Br WF o 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 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 59.72 0 0.20 1.47 0.30 Comparative Example 1 22.84 15.22 0 0 0 0 0.21 0 0 Comparative Example 2 22.84 7.61 7.61 0 0 61.73 0 0.21 0 0

As shown in Table 2 and Table 3, 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.

 [Example 10]

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. And when ZnCl, NaCl, and KCl are in a molar ratio of 60:20:20,

 2

 These powders were weighed in a glove box under an Ar atmosphere, and then stored in an alumina crucible in the same glove box.

[0109] Also, a mixture of ZnCl, NaCl, and KC1 contained in the above-mentioned alumina crucible 100 mol

 2

 For KF 4 mol and MoCl (molybdenum trichloride) 0.54 mol

 Three

 Each of these powders was weighed in a glove box, and then these powders were accommodated in the alumina crucible. Table 4 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.

 [0110] And ZnCl, NaCl, KC1, KF and MoCl are housed in the above glove box

 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.

[0111] Then, in the above glove box, a mirror-polished nickel plate with an arithmetic average roughness Ra of less than 10 nm as a cathode, a tungsten rod with a diameter of 5 mm as an anode, and a zinc rod with a diameter of 5 mm as a reference electrode Was immersed in the molten salt bath of Example 11. Next, in a state where the temperature of the molten salt bath is maintained at 250 ° C., the three-electrode method for controlling the potential of the nickel plate as the cathode is set to 150 mV between the cathode and the anode. By conducting the electrolysis in (Table 6), a precipitate containing molybdenum was obtained on the surface of the nickel plate as the cathode.

[0112] Thereafter, the precipitation state, composition, surface roughness and density of the precipitates were evaluated in the same manner as in Example 1. In addition, 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.

 The results are shown in Table 6.

 Relative density of precipitates (%) = 100 X (density of precipitates) Z (original density of molybdenum) [0113] As shown in Table 6, the precipitates obtained using the molten salt bath of Example 11 (Thickness 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.

[0114] (Example 12)

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. And when ZnCl, NaCl, and KCl are in a molar ratio of 60:20:20,

 2

 These powders were weighed in a glove box under an Ar atmosphere, and then stored in an alumina crucible in the same glove box.

[0115] In addition, a mixture of ZnCl, NaCl, and KC1 contained in the above-described alumina crucible 100 mol

 2

 For KF 4 mol and MoCl (molybdenum pentachloride) 0.54 mol

 Five

 These powders were weighed in a glove box, and then stored in the above-mentioned alumina crucible. Table 4 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.

 [0116] And in the above glove box, ZnCl, NaCl, KC1, KF and MoCl are housed.

 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.

[0117] Then, in the above glove box, a mirror-polished nickel plate with an arithmetic average roughness Ra of less than 10 nm as a cathode, a tungsten rod with a diameter of 5 mm as an anode, and a zinc rod with a diameter of 5 mm as a reference electrode Was immersed in the molten salt bath of Example 12. Next, in a state where the temperature of the molten salt bath is maintained at 250 ° C., the three-electrode method for controlling the potential of the nickel plate as the cathode is set to 150 mV between the cathode and the anode. By performing electrolysis in (Table 6), a precipitate containing molybdenum was obtained on the surface of the nickel plate as the cathode.

[0118] 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.

 [0120] (Example 13)

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. Also, the WO powder is dried in a vacuum oven at 100 ° C for 12 hours.

 Three

 It was. And when ZnCl, NaCl, and KCl have a molar ratio of 60:20:20,

 2

 Each of these powders was weighed in a glove box, and then stored in an alumina crucible in the same glove box.

[0121] Further, a mixture of ZnCl, NaCl, and KC1 contained in the above-described alumina crucible 100 mol

 2

 Against KF force mol, WO to 0.54 mol in the above glove box

 Three

 After weighing each of these powders, these powders were stored in the above-mentioned alumina crucible. Table 4 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.

[0122] Then, ZnCl, NaCl, KC1, KF and WO are accommodated in the glove box.

 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.

[0123] Then, in the above glove box, 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 13. Next, while maintaining the temperature of this molten salt bath at 250 ° C, the potential of the cathode and the anode is controlled by the three-electrode method that controls the potential of the nickel plate, which is the cathode. By performing electrolysis in (Table 6), a precipitate containing tungsten was obtained on the surface of the nickel plate as the cathode.

 [0124] Thereafter, evaluation was performed in the same manner as in Example 1 on the precipitation state, composition, surface roughness, density, and relative density of the precipitates. The results are shown in Table 6.

[0125] As shown in Table 6, 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. [Example 14]

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. And when ZnCl, NaCl, and KCl are in a molar ratio of 60:20:20,

 2

 These powders were weighed in a glove box under an Ar atmosphere, and then stored in an alumina crucible in the same glove box.

[0127] In addition, a mixture of ZnCl, NaCl, and KC1 contained in the above-described alumina crucible 100 mol

 2

 For KF force mol and Ta O (ditantalum pentoxide) 0.55 mol

 twenty five

 Each of these powders was weighed in a glove box, and then these powders were accommodated in the above-mentioned alumina crucible. Shows the composition (molar ratio) of raw materials stored in alumina crucible.

Shown in 4.

 [0128] And ZnCl, NaCl, KC1, KF and Ta O are accommodated in the above glove box.

 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.

[0129] Then, in the above glove box, a mirror-polished nickel plate with an arithmetic average roughness Ra of less than 10 nm as a cathode, a tungsten rod with a diameter of 5 mm as an anode, and a zinc rod with a diameter of 5 mm as a reference electrode Was immersed in the molten salt bath of Example 14. Next, while maintaining the temperature of this molten salt bath at 250 ° C, the potential of the cathode and the anode is controlled by the three-electrode method that controls the potential of the nickel plate, which is the cathode. By performing electrolysis in (Table 6), a precipitate containing tantalum was obtained on the surface of the nickel plate as the cathode.

[0130] Thereafter, the precipitation state, composition, surface roughness and density of the precipitates were evaluated in the same manner as in Example 1. In addition, 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.

 The results are shown in Table 6.

 Relative density of precipitates (%) = 100 X (Precipitate density) Z (Original density of tantalum)

[0131] As shown in Table 6, precipitates (thickness 0.5 / zm) obtained using the molten salt bath of Example 14 The precipitate was in the form of a film, had a high tantalum content and high purity, and had a high density, a high relative density and a high density with a small surface roughness.

 [Example 15]

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. And when ZnCl, NaCl, and KCl are in a molar ratio of 60:20:20,

 2

 These powders were weighed in a glove box under an Ar atmosphere, and then stored in an alumina crucible in the same glove box.

[0133] Further, a mixture of ZnCl, NaCl, and KC1 contained in the above-described alumina crucible 100 mol

 2

 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.

[0134] Continue! In the above glove box, ZnCl, NaCl, KC1 and KF were stored.

 2

 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

 2

 TiCl is weighed in the above glove box, and the weighed TiCl is

 4 4

 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.

[0135] Then, in the above glove box, 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. Next, while maintaining the temperature of the molten salt bath at 250 ° C, 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. By performing electrolysis in (Table 6), a precipitate containing titanium was obtained on the surface of the nickel plate as the cathode.

[0136] Thereafter, the precipitation state, composition, surface roughness and density of the precipitates were evaluated in the same manner as in Example 1. In addition, 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 results are shown in Table 6.

 Relative density of precipitates (%) = 100 X (precipitate density) Z (original density of titanium)

[0137] As shown in Table 6, the precipitate (thickness 0.1 μm) 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.

[Example 16]

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. And when ZnCl, NaCl, and KCl are in a molar ratio of 60:20:20,

 2

 These powders were weighed in a glove box under an Ar atmosphere, and then stored in an alumina crucible in the same glove box.

[0139] Further, a mixture of ZnCl, NaCl, and KC1 contained in the above-mentioned alumina crucible 100 mol

 2

 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.

[0140] Continue! In the above glove box, ZnCl, NaCl, KC1 and KF are stored.

 2

 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.

 2

 TiCl is weighed in the above glove box and the weighed TiCl is

 4 4

 By adding it into the crucible, 500 g of the molten salt bath of Example 16 was produced. 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.

[0141] Then, in the above glove box, 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. Next, while maintaining the temperature of this molten salt bath at 250 ° C, 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. By performing the electrolysis in (Table 6), a precipitate containing titanium is obtained on the surface of the nickel plate as the cathode. [0142] Thereafter, the precipitation state, composition, surface roughness, density and relative density of the precipitates were evaluated in the same manner as in Example 15. The results are shown in Table 6.

 [0143] As shown in Table 6, the precipitate (thickness 0.1 μm) 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.

 [Example 17]

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. And when ZnCl, NaCl, and KCl are in a molar ratio of 60:20:20,

 2

 These powders were weighed in a glove box under an Ar atmosphere, and then stored in an alumina crucible in the same glove box.

[0145] In addition, a mixture of ZnCl, NaCl, and KC1 contained in the above-described alumina crucible 100 mol

 2

 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.

[0146] Continue! In the above glove box, ZnCl, NaCl, KC1 and KF are stored.

 2

 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.

 2

 TiCl is weighed in the above glove box and the weighed TiCl is

 4 4

 By adding it into the crucible, 500 g of the molten salt bath of Example 17 was produced. 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.

[0147] Then, in the above-mentioned glove box, as a cathode, a mirror-polished nickel plate with an arithmetic average roughness Ra of less than lOnm, a tungsten rod with a diameter of 5 mm as an anode, and a zinc rod with a diameter of 5 mm as a reference electrode Was immersed in the molten salt bath of Example 17. Next, while maintaining the temperature of this molten salt bath at 250 ° C, the potential of the nickel plate, which is the cathode, is controlled by the three-electrode method, with the potential between the cathode and the anode set to 60 mV, and the electrolysis conditions for 8 hours. By performing electrolysis in (Table 6), a precipitate containing titanium was obtained on the surface of the nickel plate as the cathode.

[0148] Thereafter, the precipitation state, composition, surface roughness, density and density of the precipitates were determined in the same manner as in Example 15. The relative density was evaluated. The results are shown in Table 6.

[0149] As shown in Table 6, 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.

[0150] (Example 18)

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. And when ZnCl, NaCl, and KCl are in a molar ratio of 60:20:20,

 2

 These powders were weighed in a glove box under an Ar atmosphere, and then stored in an alumina crucible in the same glove box.

[0151] In addition, a mixture of ZnCl, NaCl, and KC1 contained in the above-described alumina crucible 100 mol

 2

 In contrast, the above-mentioned gloss is adjusted so that KF is 4 mol and NbCl (niobium pentachloride) is 0.54 mol.

 Five

 Each of these powders was weighed in a tube box, and then these powders were accommodated in the alumina crucible. Table 4 shows the composition (molar ratio) of the raw materials contained in the alumina crucible.

 [0152] And ZnCl, NaCl, KC1, KF and NbCl are housed in the above glove box

 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.

[0153] Then, in the above glove box, as a cathode, a mirror-polished nickel plate having an arithmetic average roughness Ra of less than lOnm, 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 18. Next, while maintaining the temperature of this molten salt bath at 250 ° C, the potential of the cathode and the anode is controlled by the three-electrode method that controls the potential of the nickel plate, which is the cathode. By performing electrolysis in (Table 6), a precipitate containing niobium was obtained on the surface of the nickel plate as the cathode.

[0154] Thereafter, the precipitation state, composition, surface roughness and density of the precipitates were evaluated in the same manner as in Example 1. In addition, 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 results are shown in Table 6.

 Relative density of precipitates (%) = 100 X (precipitate density) Z (original density of niobium)

[0155] As shown in Table 6, 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.

[Example 19]

 Each powder of ZnCl, NaCl, KC1 and KF is placed in a vacuum oven at 200 ° C.

2

 Let dry for hours. And when ZnCl, NaCl, and KCl are in a molar ratio of 60:20:20,

 2

 These powders were weighed in a glove box under an Ar atmosphere, and then stored in an alumina crucible in the same glove box.

[0157] Further, a mixture of ZnCl, NaCl, and KC1 contained in the above-mentioned alumina crucible 100 mol

 2

 In contrast, KF is 4 mol and VC1 (vanadium dichloride) is 0.54 mol.

 2

 Each of these powders was weighed in a glove box, and then these powders were accommodated in the above-mentioned alumina crucible. Shows the composition (molar ratio) of raw materials stored in alumina crucible.

Shown in 4.

 [0158] And ZnCl, NaCl, KC1, KF and VC1 are housed in the above glove box.

 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.

[0159] Then, in the above glove box, 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 19. Next, while maintaining the temperature of this molten salt bath at 250 ° C, the potential of the cathode and the anode is controlled by the three-electrode method that controls the potential of the nickel plate, which is the cathode. By performing electrolysis in (Table 6), a precipitate containing vanadium was obtained on the surface of the nickel plate as the cathode.

[0160] Thereafter, the precipitation state, composition, surface roughness and density of the precipitates were evaluated in the same manner as in Example 1. Also intended to precipitate the relative density of precipitates The original density of the vanadium metal is 6. ll (g / cm ³ ), and the relative density (%) of the precipitate is calculated from the calculated density of the precipitate and the original density of the vanadium by the following formula. Lumo of composition (ratio)

 Was calculated. The results are shown in Table 6.

 Example 11

[0161] Precipitates obtained using the molten salt bath shown in Table 6 (thickness 0.5 / z m)

 As in Example 12, the solution of Example 19

 The precipitation state is the film form of Example 13, the amount of vanadium is high purity, the surface roughness is small,

 Example 14

 It was a high density, high relative density practical example 15 and a highly dense precipitate.

 Example 16

[0162] [Table 4]

 Example 17

 Example 18

 Example 91

 o o o o o o o

 > ο

 Ma

 o o o o o o o ο

 o

 Size

 o in

 o o o o ο

 o csi o

 CO o o o o o o o ο

 1—o

O o o in o o o o o ο

 o o LO ο

 o o o o

 o o o o o o o o ο

 o

 o Mamao CO o o o o o o o o o ο

 CSJ CSJ CSJ o o o O o o o o

 CO CM C CM o O O o o o o o o

CO CO O CO CO sffi molten salt bath composition (atomic

0164 Zn Na K CI O F W Mo Ta Ti Nb V

 Example 11 22.21 7.40 8.88 59.82 0 1.48 0 0.20 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 0.20 0 Example 19 22.25 7.42 8.90 59.74 0 1.48 0 0 0 0 0 0.20

^ s Electrolytic conditions Precipitate

 Composition (Atom) Surface Relative Potential Time Precipitation Density

 Its roughness density

(° C) (mV) (Time) State W Mo Ta Ti Nb V Ζπ O (g / cm ³ )

other (%)

Example 11 250 150 3 Film-like 0 99 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 1.7 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 0.1 0.8 1.9 15.1 90.7 Example 15 250 60 6 Film type 0 0 0 99 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 98.9 0 0 0 0.3 0.8 2.3 4.1 90.3 Example 18 250 60 3 Film 0 0 0 0 99.1 0 0 0.1 0.8 3.2 8.1 94.5 Example 19 250 60 3 Film 0 0 0 0 0 98.2 0 0.5 1.3 2.6 5.8 94.9

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 μm. 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 μm striped resist pattern was formed.

[0166] Then, in the glove box under an Ar atmosphere, 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.

 [0167] After the constant current electrolysis, 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. Subsequently, after drying the silicon substrate, a plasma using a mixed gas of CF (carbon tetrafluoride) and O (oxygen) is used.

 4 2

 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.

[0168] The embodiments and examples disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

 Industrial applicability

[0169] 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. When the molten salt bath of the present invention is used, a precipitate having a high purity, high density and high density and a smooth surface can be obtained.

Claims

 The scope of the claims

 [I] A group salt consisting of chlorine, bromine and iodine A molten salt bath containing at least one selected, zinc, at least two alkali metals, and fluorine.

 [2] The molten salt bath according to claim 1, which contains oxygen.

 [3] tungsten, chromium, molybdenum, tantalum, titanium, zirconium, vanadium, hough

The molten salt bath according to claim 1, characterized in that it contains at least one selected from the group consisting of -um and niobium.

[4] It is characterized in that at least two kinds of group power consisting of sodium, potassium and cesium are selected as the alkali metal, at least one of chlorine and bromine, zinc and fluorine are used. The molten salt bath according to claim 1.

[5] The molten salt bath according to claim 1, wherein the zinc content is 14 atomic% or more and 30 atomic% or less of the entire molten salt bath.

6. The molten salt bath according to claim 1, wherein the zinc content is 17 atomic% or more and 25 atomic% or less of the entire molten salt bath.

7. The molten salt bath according to claim 1, wherein the fluorine content is 0.1 atomic% or more and 20 atomic% or less of the entire molten salt bath.

[8] A precipitate obtained using the molten salt bath according to claim 1.

 [9] The precipitate according to claim 8, wherein the molten salt bath is precipitated in a state containing 0.01 atomic% or more of oxygen.

[10] The precipitate according to claim 8, wherein the arithmetic average roughness Ra FIS B0601-1994) of the surface of the precipitate is as follows.

 [II] The precipitate according to claim 8, wherein the relative density of the precipitate is 85% or more.

 [12] The step of forming a resist pattern on the conductive substrate to expose a part of the conductive substrate; and the conductive substrate on which the resist pattern is formed are immersed in the molten salt bath according to claim 1. A method for producing a metal product, comprising: a step; and a step of depositing a metal from the molten salt bath on an exposed portion of the conductive substrate.

[13] The gold according to claim 12, wherein the temperature of the molten salt bath is 250 ° C or lower. A method of manufacturing a genus product.

 A metal product manufactured using the method for manufacturing a metal product according to claim 13.