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US20120031764A1 - Microcrystalline-to-amorphous gold alloy and plated film, and plating solution for those, and plated film formation method - Google Patents

Microcrystalline-to-amorphous gold alloy and plated film, and plating solution for those, and plated film formation method Download PDF

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Publication number
US20120031764A1
US20120031764A1 US13/202,050 US201013202050A US2012031764A1 US 20120031764 A1 US20120031764 A1 US 20120031764A1 US 201013202050 A US201013202050 A US 201013202050A US 2012031764 A1 US2012031764 A1 US 2012031764A1
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Prior art keywords
plated film
amorphous
gold alloy
microcrystalline
gold
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Inventor
Tetsuya Osaka
Yutaka Okinaka
Kazutaka Senda
Ryota Iwai
Masaru Kato
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Kanto Chemical Co Inc
Waseda University
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Kanto Chemical Co Inc
Waseda University
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Assigned to WASEDA UNIVERSITY, KANTO KAGAKU KABUSHIKI KAISHA reassignment WASEDA UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OKINAKA, YUTAKA, IWAI, RYOTA, KATO, MASARU, SENDA, KAZUTAKA, OSAKA, TETSUYA
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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
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated

Definitions

  • the present invention relates to a mixed microcrystalline-amorphous gold alloy plated film that is useful as a plated film for a terminal of an electronic equipment component and has excellent electrical properties and mechanical properties, an electroplating solution that can form this mixed microcrystalline-amorphous gold alloy plated film, and an electroplating method employing this electroplating solution.
  • a gold plated film As an electrical contact material for, in particular, parts where high reliability is required in an electrical/electronic component connector, a miniature electromechanical relay, a printed wiring board, etc., a gold plated film called a hard gold plated film is currently widely used.
  • the hard gold plated film has cobalt, nickel, etc. added to gold, and its film hardness is improved without reducing the intrinsically good electrical conductivity and chemical stability of gold.
  • This hard gold plated film has a fine structure in which gold microcrystals (20 to 30 nm) are aggregated, and it is surmised that, in accordance with this fine structure, a hardness (on the order of Hk 170 as a Knoop hardness) that is the minimum requirement for obtaining the abrasion resistance required for the contact material is obtained.
  • the present invention has been accomplished in light of the above-mentioned circumstances, and it is an object thereof to provide a mixed microcrystalline-amorphous gold alloy plated film having improved hardness and excellent abrasion resistance while having good electrical conductivity and chemical stability, an electroplating solution that can form this mixed microcrystalline-amorphous gold alloy plated film, and an electroplating method employing this electroplating solution.
  • an amorphous phase structure can improve the hardness and abrasion resistance while the intrinsically good specific resistance and chemical stability of gold are maintained to such a degree that there are no problems in practice, but since the electron mean free path is shorter than in a crystalline film, electroconductivity is low, and cracks are easily generated in a plated film by internal stress; it has been found that, in accordance with electroplating using an electroplating solution having good liquid stability, containing at a predetermined concentration a gold cyanide salt, and a nickel salt and/or a cobalt salt, and preferably further containing a complexing agent such as an organic acid, an inorganic acid, or a salt thereof and ammonia or ammonium ion, a mixed microcrystalline-
  • the present invention provides (1) a mixed microcrystalline-amorphous gold alloy plated film that is formed so that a microcrystalline phase and an amorphous phase are mixed, (2) an electroplating solution, having good liquid stability, containing a gold cyanide salt at a concentration of 0.0001 to 0.4 mol/dm 3 on a gold basis, and a nickel salt at a concentration of 0.001 to 0.5 mol/dm 3 on a nickel basis and/or a cobalt salt at a concentration of 0.001 to 0.5 mol/dm 3 on a cobalt basis, and preferably further containing a complexing agent such as an organic acid, an inorganic acid, or a salt thereof at a concentration of 0.001 to 2.0 mol/dm 3 and ammonia or ammonium ion at a concentration of 0.001 to 5.0 mol/dm 3 , and (3) an electroplating method in which a mixed microcrystalline-amorphous gold alloy plated film is formed on an article to be plated using this
  • the mixed microcrystalline-amorphous gold alloy plated film of the present invention is formed so that a microcrystalline phase and an amorphous phase are mixed; as a result the hardness is improved while the intrinsically good specific resistance value and chemical stability of gold are maintained to a degree that is useful in practice, and it is useful as a contact material for an electrical/electronic component such as a relay.
  • an electrical/electronic component such as a relay. It is known that, in general, in the constituent case of a crystalline film formed from microcrystals, when the crystalline particles reduce in size, the hardness increases up to a certain limit (e.g. about 4 nm in the case of nickel), but when the crystalline particles further reduce in size the hardness is degraded.
  • the mixed microcrystalline-amorphous gold alloy plated film solves all such problems, has high electrical conductivity, and is resistant to cracking, thus making it fully applicable as a microcontact material for an electrical/electronic component such as a connector or a relay.
  • FIG. 1 A diagram showing XRD patterns of mixed microcrystalline-amorphous gold alloy plated films obtained in Examples 1, 2, 3, 4, and 5 and gold alloy plated films obtained in Comparative Examples 1 and 2.
  • FIG. 2 A diagram showing a TEM image (100,000 ⁇ ) of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 1.
  • FIG. 3 A diagram showing a TEM image (1,000,000 ⁇ ) of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 1.
  • FIG. 4 A diagram showing a TREED pattern of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 1.
  • FIG. 5 A diagram showing a TEM image (500,000 ⁇ ) of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 2.
  • FIG. 6 A diagram showing a TEM image (1,000,000 ⁇ ) of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 2.
  • FIG. 7 A diagram showing a TREED pattern of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 2.
  • FIG. 8 A diagram showing a TEM image (300,000 ⁇ ) of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 3.
  • FIG. 9 A diagram showing a TEM image (1,000,000 ⁇ ) of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 3.
  • FIG. 10 A diagram showing a THEED pattern of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 3.
  • FIG. 11 A diagram showing a TEM image (200,000 ⁇ ) of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 4.
  • FIG. 12 A diagram showing a TEM image (700,000 ⁇ ) of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 4.
  • FIG. 13 A diagram showing a TREED pattern of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 4.
  • FIG. 14 A diagram showing a TEM image (400,000 ⁇ ) of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 5.
  • FIG. 15 A diagram showing a TEM image (1,000,000 ⁇ ) of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 5.
  • FIG. 16 A diagram showing of a TREED pattern of the mixed microcrystalline-amorphous gold alloy plated film obtained in Example 5.
  • FIG. 17 A diagram showing a TEM image (1,000,000 ⁇ ) of the amorphous gold alloy plated film obtained in Comparative Example 1.
  • FIG. 18 A diagram showing a THEED pattern of the amorphous gold alloy plated film obtained in Comparative Example 1.
  • the mixed microcrystalline-amorphous gold alloy plated film of the present invention is formed so that a microcrystalline phase and an amorphous phase are mixed.
  • the mixed microcrystalline-amorphous gold alloy plated film of the present invention contains nickel and/or cobalt in gold, its fine structure is a structure in which a microcrystalline phase and an amorphous phase are mixed, and in accordance with these characteristics, a good specific resistance value and chemical stability as well as high hardness can be achieved compared with an amorphous gold alloy plated film having a pure amorphous structure.
  • Such a structure in which a microcrystalline phase and an amorphous phase are mixed can be confirmed by an X-ray diffraction (XRD) pattern, a transmission electron microscope (TEM) image, and a transmission high energy electron diffraction (THEED) image.
  • the mixed microcrystalline-amorphous gold alloy plated film of the present invention has an average microcrystal particle size of no greater than 30 nm, particularly no greater than 20 nm, and more particularly no greater than 15 nm.
  • the mixed microcrystalline-amorphous gold alloy plated film of the present invention has a microcrystal volume fraction of 10% to 90%, and particularly 15% to 60%.
  • a mixed microcrystalline-amorphous gold alloy plated film having excellent hardness and specific resistance such that the Knoop hardness is at least Hk 180, particularly at least Hk 220, further at least Hk 300, and yet further at least Hk 350, and the specific resistance is no greater than 200 ⁇ cm, particularly no greater than 150 ⁇ cm, and yet further no greater than 100 ⁇ cm can be obtained.
  • the structure in which a microcrystalline phase and an amorphous phase are mixed will not be changed (that is, crystallization progressing and the microcrystal average particle size or volume fraction increasing) by annealing at no greater than 300° C. (kept for 1 hour).
  • the mixed microcrystalline-amorphous gold alloy plated film of the present invention has characteristics of high hardness, which is not possessed by a conventional gold or gold alloy plated film, together with its excellent specific resistance value and chemical stability, it is effective as a conductive contact such as a terminal of an electrical/electronic component such as an electromagnetic switch, a breaker, a thermostat, a relay, a timer, various types of switches, or a printed wiring board.
  • an electrical/electronic component such as an electromagnetic switch, a breaker, a thermostat, a relay, a timer, various types of switches, or a printed wiring board.
  • the mixed microcrystalline-amorphous gold alloy plated film of the present invention may be represented by the compositional formula Au 100-x-y M x C y , wherein Au or M is a main component, inevitable impurities may be contained, M is Ni and/or Co, C is carbon, 1 atom % ⁇ x ⁇ 80 atom %, and 1 atom % ⁇ y ⁇ 30 atom %.
  • the mixed microcrystalline-amorphous gold alloy plated film of the present invention may be formed by electroplating using an electroplating solution containing a gold cyanide salt, and a nickel salt and/or a cobalt salt.
  • This electroplating solution contains a gold cyanide salt, and a nickel salt and/or a cobalt salt; specific examples of the gold cyanide salt include gold potassium cyanide, gold sodium cyanide, and gold lithium cyanide, specific examples of the nickel salt include nickel sulfate and nickel nitrate, and specific examples of the cobalt salt include cobalt sulfate and cobalt nitrate.
  • the gold cyanide salt concentration of the plating solution is 0.0001 to 0.4 mol/dm 3 on a gold basis, preferably 0.001 to 0.2 mol/dm 3 , and more preferably 0.01 to 0.1 mol/dm 3
  • the nickel salt concentration is 0.001 to 0.5 mol/dm 3 on a nickel basis, and preferably 0.01 to 0.2 mol/dm 3
  • the cobalt salt concentration is 0.001 to 0.5 mol/dm 3 on a cobalt basis, and preferably 0.01 to 0.2 mol/dm 3 .
  • the ratio [(Ni+Co)/Au] of nickel and/or cobalt to gold in the plating solution is preferably in the range of 0.01 to 300 as a molar ratio, and more preferably 1 to 30.
  • this electroplating solution preferably further contains a complexing agent.
  • this complexing agent include an organic acid, inorganic acid, or salt thereof that has a complexing action and a pH buffering action, and examples of the organic acid, inorganic acid, and salt thereof include citric acid, tartaric acid, malic acid, pyrophosphoric acid, phosphoric acid, sulfamic acid, and sodium, potassium, and ammonium salts thereof.
  • concentration of the complexing agent in the plating solution is 0.001 to 2.0 mol/dm 3 , particularly 0.01 to 1.0 mol/dm 3 , and more particularly 0.1 to 0.3 mol/dm 3 .
  • the ratio [complexing agent/(Ni+Co)] of the complexing agent to nickel and/or cobalt in the plating solution is preferably in the range of 0.01 to 100 as a molar ratio, and more preferably 1 to 4.
  • this electroplating solution preferably further contains ammonia or ammonium ion.
  • the ammonia or ammonium ion include aqueous ammonia, ammonium sulfate, and an ammonium salt of the complexing agent. It is preferable that the concentration of ammonia or ammonium ion in the plating solution is 0.001 to 5.0 mol/dm 3 , and particularly 0.01 to 2.0 mol/dm 3 . This ammonia is heavily involved in the crystallization state of a plated film, such as the average particle size of the crystalline phase or the microcrystalline (or amorphous) volume fraction, and the stability of a plating bath.
  • this electroplating solution preferably has a pH of 3 to 11, particularly a pH of 5 to 9, and more particularly a pH of on the order of 6.
  • a conventionally known pH adjusting agent such as aqueous ammonia or potassium hydroxide may be used.
  • this electroplating solution may contain as necessary various types of additives such as a surfactant and a solvent for the purpose of improving the gloss, preventing pits, imparting electrical conductivity, imparting buffering properties, increasing the range of current density that can be used, promoting the deposition rate, improving heat resistance, improving wettability, etc. as long as the film physical properties of a plated film (microcrystalline volume fraction and average particle size, XRD pattern peak half-width, Knoop hardness, specific resistance) and film composition are not greatly affected (ref. e.g. JP, A, 7-11476, JP, A, 2004-76026, JP, A, 2006-37164).
  • additives such as a surfactant and a solvent for the purpose of improving the gloss, preventing pits, imparting electrical conductivity, imparting buffering properties, increasing the range of current density that can be used, promoting the deposition rate, improving heat resistance, improving wettability, etc. as long as the film physical properties of a plated film (microcrystalline volume fraction
  • the electroplating conditions are not particularly limited, but it is desirable that the plating temperature is 20° C. to 95° C., and particularly 50° C. to 90° C.
  • the cathode current density depends on the composition of the plating solution and is not particularly limited, and a mixed microcrystalline-amorphous gold alloy plated film may be obtained in both a low current density region (e.g. at least 1 mA/cm 2 but less than 10 mA/cm 2 ) and a high current density region (e.g. greater than 10 mA/cm 2 but no greater than 200 mA/cm 2 ).
  • an insoluble anode such as platinum may be used as anode.
  • nickel and/or cobalt may be used as an anode.
  • a metal material such as copper or nickel used for electrical wiring can be cited. This metal material may be one formed as a base layer on a metal substrate or a non-metal substrate.
  • stirring may or may not be present, plating is preferably carried out under stirring, and electric current may be applied by pulse current.
  • a mixed microcrystalline-amorphous gold alloy plated film (film thickness 1 ⁇ m) was formed on a copper plate having a purity of 99.96% at a temperature of 70° C. and a current density of 10 mA/cm 2 using an electroplating solution containing 0.035 mol/dm 3 of KAu(CN) 2 , 0.076 mol/dm 3 of NiSO 4 .6H 2 O, and 0.21 mol/dm 3 of triammonium citrate and having a pH adjusted to 6 with KOH and sulfuric acid.
  • As the anode a platinum-coated titanium electrode (mesh form) was used, and the plating bath was vigorously stirred during plating.
  • the mixed microcrystalline-amorphous gold alloy plated film thus obtained was analyzed by XRD, TEM, and THEED.
  • An XRD pattern is shown in FIG. 1
  • TEM images and a THEED pattern are shown in FIGS. 2 to 4 .
  • a broad peak having a peak half-width of 1 degree or greater, which is characteristic of being microcrystalline or amorphous, was observed in the XRD pattern at around 2 ⁇ 40 degrees.
  • TEM image a state in which crystal fringes characteristic of being crystalline and an irregular structure characteristic of being amorphous are mixed could be observed.
  • the THEED pattern a state in which a diffraction spot characteristic of being crystalline and a halo ring characteristic of being amorphous are mixed could be observed.
  • the plated film obtained had a mixed microcrystalline-amorphous structure. Furthermore, as a result of examining the TEM image, the average particle size of the microcrystals was found to be 10 nm, and the volume fraction of the microcrystalline phase was 50%. Separately, the compositional analysis, Knoop hardness, and specific resistance of the mixed microcrystalline-amorphous gold alloy plated film obtained were measured. As metal elements gold was detected at a content of 41.2 atom % and nickel was at 46.0 atom %, and as a non-metal element carbon was detected at a content of 12.8 atom %. The Knoop hardness was Hk 347, and the specific resistance was 89 ⁇ cm.
  • Plating was carried out in the same way as for Example 1 except that n-propanol was added at 20 vol %, and the plated film thus obtained was subjected to XRD, TEM, and THEED analyses.
  • An XRD pattern is shown in FIG. 1
  • TEM images and a THEED pattern are shown in FIGS. 5 to 7 .
  • a broad peak having a peak half-width of 1 degree or greater, which is characteristic of being microcrystalline or amorphous, was observed in the XRD pattern at around 2 ⁇ 40 degrees.
  • TEM image a state in which crystal fringes characteristic of being crystalline and an irregular structure characteristic of being amorphous are mixed could be observed.
  • the plated film obtained had a mixed microcrystalline-amorphous structure. Furthermore, as a result of examining the TEM image, the average particle size of the microcrystals was found to be 10 nm, and the volume fraction of the microcrystalline phase was 50%. Separately, the compositional analysis, Knoop hardness, and specific resistance of the mixed microcrystalline-amorphous gold alloy plated film obtained were measured.
  • Plating was carried out in the same way as for Example 1 except for a concentration of citric acid of 0.143 mol/dm 3 , a concentration of ammonia of 1.2 mol/dm 3 , and electroplating being carried out alternatingly at current densities of 1 mA/cm 2 (application time 50 sec) and 10 mA/cm 2 (application time 5 sec) without a gap, and the plated film thus obtained was subjected to XRD, TEM, and THEED analyses. An XRD pattern is shown in FIG. 1 , and TEM images and a THEED pattern are shown in FIGS. 8 to 10 .
  • a broad peak having a peak half-width of 1 degree or greater, which is characteristic of being microcrystalline or amorphous, was observed in the XRD pattern at around 2 ⁇ 40 degrees. Furthermore, in the TEM image a state in which crystal fringes characteristic of being crystalline and an irregular structure characteristic of being amorphous are mixed could be observed. In the TREED pattern, a state in which a diffraction spot characteristic of being crystalline and a halo ring characteristic of being amorphous are mixed could be observed. In the case of constant-current plating, only a crystalline phase was obtained at a current density of 1 mA/cm 2 , and only an amorphous phase was obtained at 10 mA/cm 2 .
  • the plated film obtained by pulse plating had a mixed microcrystalline-amorphous structure. Furthermore, as a result of examining the TEM image, the average particle size of the microcrystals was found to be 10 nm, and the volume fraction of the microcrystalline phase was 60%. Separately, the compositional analysis, Knoop hardness, and specific resistance of the plated film obtained were measured. As metal elements gold was detected at a content of 47.4 atom % and nickel was at 47.0 atom %, and as a non-metal element carbon was detected at a content of 5.6 atom %. The Knoop hardness was Hk 222, and the specific resistance was 57 ⁇ cm.
  • Plating was carried out in the same way as for Example 1 except for a concentration of citric acid of 0.143 mol/dm 3 , a concentration of ammonia of 1.2 mol/dm 3 , and a current density of 50 mA/cm 2 , and a plated film obtained by subjecting the amorphous gold alloy plated film thus obtained to an annealing treatment at an annealing temperature (holding temperature) of 400° C., a rate of temperature increase of 10° C./min, temperature held for 1 hour, under an air atmosphere was subjected to XRD, TEM, and THEED analyses. An XRD pattern is shown in FIG. 1 , and TEM images and a THEED pattern are shown in FIGS. 11 to 13 .
  • a broad peak having a peak half-width of 1 degree or greater, which is characteristic of being microcrystalline or amorphous, was observed in the XRD pattern at around 2 ⁇ 40 degrees. Furthermore, in the TEM image a state in which crystal fringes characteristic of being crystalline and an irregular structure characteristic of being amorphous are mixed could be observed. In the THEED pattern, a state in which a diffraction spot characteristic of being crystalline and a halo ring characteristic of being amorphous are mixed could be observed. From these results, it can be seen that the plated film obtained had a mixed microcrystalline-amorphous structure. Furthermore, as a result of examining the TEM image, the average particle size of the microcrystals was found to be 15 nm, and the volume fraction of the microcrystalline phase was 60%.
  • a mixed microcrystalline-amorphous gold alloy plated film (film thickness 1 ⁇ m) was formed on a copper plate having a purity of 99.96% at a temperature of 70° C. and a current density of 10 mA/cm 2 using an electroplating solution containing 0.035 mol/dm 3 of KAu(CN) 2 , 0.076 mol/dm 3 of CoSO 4 .7H 2 O, and 0.1 mol/dm 3 of citric acid.H 2 O, having an ammonia concentration of 0.44 mol/dm 3 , and having a pH adjusted to 6 with KOH and sulfuric acid.
  • As the anode a platinum-coated titanium electrode (mesh form) was used, and the plating bath was vigorously stirred during plating.
  • the mixed microcrystalline-amorphous gold alloy plated film thus obtained was analyzed by XRD, TEM, and TREED.
  • An XRD pattern is shown in FIG. 1
  • TEM images and a TREED pattern are shown in FIGS. 14 to 16 .
  • a broad peak having a peak half-width of 1 degree or greater, which is characteristic of being microcrystalline or amorphous, was observed in the XRD pattern at around 2 ⁇ 40 degrees.
  • TEM image a state in which crystal fringes characteristic of being crystalline and an irregular structure characteristic of being amorphous are mixed could be observed.
  • the plated film obtained had a mixed microcrystalline-amorphous structure. Furthermore, as a result of examining the TEM image, the average particle size of the microcrystals was found to be 5 nm, and the volume fraction of the microcrystalline phase was 15%. Separately, the compositional analysis and Knoop hardness of the mixed microcrystalline-amorphous gold alloy plated film obtained were measured.
  • Plating was carried out in the same way as for Example 1 except for a concentration of citric acid of 0.143 mol/dm 3 and a concentration of ammonia of 0.46 mol/dm 3 , and the plated film thus obtained was subjected to XRD, TEM, and TREED analyses.
  • An XRD pattern is shown in FIG. 1
  • a TEM image and a THEED pattern are shown in FIGS. 17 and 18 .
  • a broad peak having a peak half-width of 1 degree or greater, which is characteristic of being amorphous, was observed in the XRD pattern at around 2 ⁇ 40 degrees.
  • the plated film obtained had a homogeneous amorphous structure without having microcrystals. Furthermore, the compositional analysis, Knoop hardness, and specific resistance of the plated film obtained were measured. As metal elements gold was detected at a content of 15.2 atom % and nickel was at 67.5 atom %, and as a non-metal element carbon was detected at a content of 17.3 atom %. The Knoop hardness was Hk 435, and the specific resistance was 251 ⁇ cm.
  • a hard gold plated film (film thickness 1 ⁇ m) was formed on a copper plate having a purity of 99.96% at a temperature of 30° C. and a current density of 10 mA/cm 2 using an electroplating solution containing 0.04 mol/dm 3 of KAu(CN) 2 , 0.0085 mol/dm 3 of NiSO 4. 6H 2 O, 0.5 mol/dm 3 of citric acid.H 2 O, and 0.7 mol/dm 3 of KOH and having a pH adjusted to 3.5 with sulfuric acid.
  • As the anode a platinum-coated titanium electrode (mesh form) was used, and the plating bath was gently stirred during plating.
  • the hard gold plated film thus obtained was analyzed by XRD, TEM, and TREED.
  • An XRD pattern is shown in FIG. 1 .
  • the average particle size of the crystals was 13 nm.
  • the Knoop hardness of additive-free hard gold (AFHG), nickel hard gold (NiHG), and CoHG which are considered to have high hardness among gold plated films, is on the order of less than Hk 200
  • the Knoop hardness of the mixed microcrystalline-amorphous gold alloy plated film of Example 1 has a high hardness corresponding to 2 to 3 times the above.

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