TW201111560A - Fine crystalline and amorphous coexisting gold alloy, plating film, plating solution, and plating method for said film - Google Patents

Abstract

Disclosed is a microcrystalline-to-amorphous gold alloy-plated film having excellent electrical properties and excellent mechanical properties. Physical properties including both the advantageous properties of a crystalline structure and the advantageous properties of an amorphous structure can be obtained by allowing a microcrystalline phase and an amorphous phase to exist in a mixed state at a specific ratio. The average particle diameter of the microcrystals is 30 nm or smaller, the volume fraction of the microcrystals is 10 to 90%, the knoop hardness is Hk 180 or more, the specific resistivity is 200 [μ]Ocm or less. In the film, hardness and abrasion resistance can be improved while maintaining a good specific resistivity value and chemical stability both inherent to gold at practically insignificant levels. Therefore, the film is useful as a material for connecting an electric or electronic component such as a connector and a relay.

Description

201111560 VI. Description of the Invention: [Technical Field] The present invention relates to an end-non-shaped hybrid gold alloy plating film which is effective for use in a mineral coating film, an electrical property and a mechanical component, ·,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Side liquid, the use of this electric property [Prior technology] In the electrical / electronic parts connector, electrical and mechanical small (four) device, printed wiring, _ is the electrical contact material for the part of the high letter Now, _ straight wide money - the species is called hard gold plating (four) gold film. The hard gold seam film is a kind of material which is added to gold, such as nickel or the like, and which does not lower the good electrical conductivity and chemical stability of gold, and can increase the hardness of the film. Such a hard gold film is a fine structure having a fine crystal of gold (2〇~3〇nm), which can be regarded as a kind of fine structure which can be obtained to obtain a contact material. The minimum hardness required for wear resistance (Knoop hardness: Hk 170 or so). On the other hand, in recent years, the size of electrical contacts has been miniaturized with the miniaturization of electronic components. However, the plating film formed in such minute contacts has been reduced in size and thinned. Therefore, it is also required to further increase the hardness upward to obtain high wearability. In addition, in the near future, the size of the contact point must be similar to the fine crystal size of the hard gold deposit film described above; in the case of forming a hard gold plating film as described above on the fine contact such as this, Since the absolute number of the fine 3/22 201111560 t曰曰 constituting the film is small, it is expected that the same resistance as in the case of the hard f-reading film formed on the joint of the currently applicable size is not obtained. Therefore, the inventors of the present invention have invented an amorphous gold alloy plating film formed by having no fine crystal phase (for example, J 6 to 8). However, it can be said that there is still room for improvement in terms of the fact that it is possible to maintain the goodness of gold as a function of electrical stability without being problematic. In the prior art, the related art document information of the present invention is as follows: [Patent Document 1] JP-A-60-33382 (Patent Document 2) JP-A-62-29-893 Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2, No. Hei. Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. 2-7-7697 No. 6 (Non-Patent Document) [Non-Patent Document 1] Chuan Hehui, "Study on Gold-Nickel Alloy Plating Handle "Metal Surface Technology, 1968, Vol. 19, No. 487-491 [Non-Patent Document 2] Shimizu Kazuo and the other, "Study on the Electron Microscope of the Fine Structure and Phase of the A-Alloy Alloy", Metal watch 〇 1 1 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , And its analytical method, technical information Yes, February 2nd, February, pp. 256-262 [Non-Patent Document 4] Xiaojian Chong and 2 others, "The high W of Ni-W alloy plating film contains conversion wealth", metal surface technology , Swollen Year, Vol. 39, Vol. 12, pp. 809-812 [Non-Patent Document 5] Watanabe Toru, "Mechanism of Forming Amorphous Alloy by Plating", Surface Technology, 1989, Vol. 40, No. [Volume 3, page 21_26] [Summary of the Invention] [Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object of the invention is to provide a good (four) conductivity and chemical stability while a fine crystal amorphous carbon alloy iron coating film excellent in hardness and abrasion resistance, an electrical mineral deposit capable of forming the fine crystal/non-shaped silk gold alloy recording film, and an electric plating solution using the same Electrical plating method. [Means for Solving the Problem] The present inventors have repeatedly and eagerly reviewed the "based system: a fine structure of a mineral coating film that does not reduce the hardness even for a minute contact, in order to achieve the above-mentioned purpose, although In contrast to the crystalline structure, the amorphous phase structure can maintain the good specific resistance and chemical stability of gold to a degree that is not problematic and can improve the hardness and the wear and tear. The average free path is shorter than the reason of the crystal film, so that the electrical conductivity is low, and due to the internal stress, the idea of cracking on the mineral film 5/22 201111560 is found, and it is found that: a liquid containing a specific concentration of orbital gold salt, _ and / or (d), the former is a further _ step of organic acids, inorganic acids or their salts, and ammonia or money ions = good electrical properties The plating solution is used for electrical plating, and a micro-junction non-shaped hybrid gold alloy money film formed by mixing a fine crystal phase and an amorphous phase can be obtained, and the film can be used for gold. Original good ratio Resisting the chemical stability while maintaining the hardness at a practically useful level is completed by further conducting the study: that is, the present invention provides: (1) a method in which a fine crystalline phase and a mixed phase are formed It is a micro-salt crystal of the dragon, a film, and (2) a nickel salt of cerium, which is _01~04_=^^, which is based on gold, and a concentrated nickel salt of m()i/dm3 on a nickel basis. And/or the riding standard is _~G.5 _ plate = salt, preferably further containing the concentration of coffee ~; t acid, inorganic acid or its salt, etc., 0 side ~ 5.0 mol / dm3 The 2 degree ammonia or the shop is used as the electric mineral of the dragon, and (3) the seed is used to make the _ electroplating solution and the material is deposited on the plated material. Electric [Effect of the Invention] The fine crystalline crystalline (10) silk gold alloy film is formed by mixing micro-recording ~ 曰 phase and shape, and the result is that it is a good ratio of gold and electrons and chemical stability. The material is kept in a material that enhances the hardness, so it can be effectively used as a contact material for the electrical/electronic parts of the article. In general, 6/22 2011 U560 = Road · In the case where the crystal film is composed of fine crystals, although the size of the crystal grains becomes small, the hardness increases to a certain limit (for example, in the case of a disorder) Bottom: about 4 nm); however, when the crystal grains are further stepped down, the hardness may be lowered. Even in the case of gold, although it is not, whether the practical example of the general theory can be applied, however, by the invention of the microcrystalline-unshaped hybrid crystal film in the gold, the first time is confirmed. The fine crystal/non-shaped mixed gold alloy plating film can completely solve the problem like the sample, and since the electric conductor is also high and is not prone to the occurrence of the turtle j, it can be sufficiently suitable as a connector. Or tiny contact materials for electrical/electronic parts such as relays. [Embodiment] Hereinafter, the present invention will be described in detail. The fine crystal-unshaped hybrid gold alloy plating film of the present invention is formed by mixing a fine crystal phase and an amorphous phase. The fine crystal-unshaped hybrid gold alloy plating film of the present invention is a material containing nickel and/or cobalt in gold' and the fine structure is a structure in which a fine crystal phase and an amorphous phase are mixed; It is achieved by other characteristics: better specific resistance, chemical stability, and higher hardness than the amorphous non-formed structure of the amorphous gold alloy plating film. Such a structure in which a fine crystal phase and an amorphous phase are mixed may be formed by an X-ray diffraction (XRD) pattern, a tooth-through electron microscope (TEM) photograph, and a transmissive high-energy electron diffraction (THEED). Photo to confirm. • The fine crystal-unshaped hybrid gold alloy plating film of the present invention has an average particle diameter of fine crystals of 3 〇 nmi §]i or less, particularly preferably 2 〇 nm, from the viewpoint of maintaining high hardness. Hereinafter, it is more preferably 15 nm or less. 7/22 201111560 Further, the fine crystal-unshaped hybrid gold alloy money coating film of the present invention, from the original gold bearing property (good specific resistance 化学 and chemical stability) or maintaining a conventional gold or gold alloy plating film From the viewpoint of the high hardness which is not obtained, the volume fraction of the fine crystals is preferably from 10 to 90%, particularly preferably from 15 to 6 % by weight. According to the present invention, it is possible to obtain a fine crystal _ amorphous carbon alloy plating film having excellent hardness and specific resistance, that is, it is possible to obtain a method having a Knoop hardness of preferably Hk 180 or more; in particular, preferably Hk 220 or more, more preferably Hk 3 〇〇 or more, particularly preferably Hk 35 〇 or more, and the specific resistance is preferably 200 μΩ · cm or less, particularly preferably 150 μΩ · cm or less, and particularly preferably 1 μ μΩ · cm or less. The film. Further, the fine crystal-unshaped hybrid gold alloy plating film of the present invention is a structure in which the annealing process (for 1 hour) is not changed, and the fine crystal phase and the amorphous phase are not mixed. , causing crystallization to increase the average particle size and volume fraction of the fine crystals. The fine crystalline-unshaped hybrid gold alloy ore film of the present invention is excellent in specific resistance and chemical stability, and has Due to the high hardness characteristics of the conventional gold or gold alloy plating film, it can be used as an electromagnetic switch, brake, thermostat, relay, timer, various switches, and printed wiring. A conductive contact of a terminal such as a terminal of an electric/electronic component such as a substrate. The fine crystal-unshaped hybrid gold alloy plating film of the present invention can have a composition formula: Au.x_yMxCy (however, Au or M is a main component and may contain Inevitable impurities; 1^ are seen and/or c〇; c is carbon; 丨 atom%$x'80 atom%; 1 atomic atom%). ^Inventive, fine crystalline-amorphous hybrid gold alloy The coating film can be used by using The electric recording liquid of cyanide gold salt, nickel salt and/or secret salt is formed by electroplating 8/22 201111560. In the electroplating solution, although it contains gold cyanide salt, nickel salt and/or Ming salt, but for example, a specific example of a gold cyanide salt may be an atmosphere = gold unloading, a gold cyanide, a gasified gold material; a specific salt of a salt; for example, a crucible may be nickel sulfate or nitric acid Nickel, etc., specific examples of the starting salt, for example, it can be recorded from sulfuric acid, coffee bars, etc. The thickness of the gold salt in the working fluid, based on gold, should be 0.0001~0.4 m〇i/ Dm3, comparison = is 〇. 001~0·2 _3, more preferably _~〇"m〇1/dm3; nickel salt wave, based on nickel, should be 0.001~0.5 mol/dm3, The parts are 〇.〇l~〇.2_/dm3; the salt concentration is calculated from the beginning, = 0.001 ~ 0.5 m_m3, preferably G G1~Q 2 mGl / dm3. Recording liquid gold and nickel and / fine At the time ((10) ridge rotation secret is 0.01~300, more preferably 1~30. X oxygen I1 raw dressing liquid, preferably further containing a wrong agent. Used as the wrong agent, For example, it can be wrong Organic acid, inorganic acid or its salt for mouth action and pH buffering; used for organic acid, no ship and salt thereof, for example, it can be a smashed wine, scorpion, malic acid "The ratio of the concentration of the complexing agent in the ore dressing liquid is preferably 0.001 to 2.0 m〇1/dm3; in particular, it is determined by the concentration of the formic acid, the acid, the amine fluoric acid and the sodium I if salt, the ammonium salt and the like. Particularly preferred is 〇〇1~]〇_i/dm3, especially preferably 0.1~0.3 molAW. The ratio of the wrong agent in the plating solution and the recording/and/or narration (missing agent / (Ni+c〇)) The molar ratio is preferably from 0.01 to 100, more preferably from 丨 to 4. Further, the electric (10) dressing preferably further contains ammonia or ammonium ions. Specific examples of the ammonia or ammonium ion used are, for example, ammonia, ammonium amide, an ammonium salt of a complexing agent, and the like. Ammonia or ammonium in the ore solution 9/22 201111560 The concentration should be 〇·_~5.0 mQl/dm3, especially for the average particle size and fine crystal of the so-called crystal phase of ~2 〇m δ hai The crystal form of the plated film of the volume fraction or the shape of the plating bath is highly correlated with the stability of the plating bath. Further, it is preferable that the pH of the electroplating solution is 3 to u; in particular, it is preferable that P "~9' is preferably about pH 6. The pH adjustment system can use a conventionally known pH such as ammonia water, potassium oxyhydroxide or the like. Further, in the electroless plating solution, the volume fraction, the average particle diameter, and the XRD pattern of the fine crystals of the plating film are not included in the electroplating solution. , #普硬,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Various kinds of additives such as an interface-active enthalpy, a granule, and the like, which are used for the purpose of the purpose of the present invention, and the like, and the like. Bulletin. Although an electric plating condition is not particularly limited, a plating temperature of 20 to 95 C, particularly 50 to 90 ° C is particularly suitable. The cathode current density also varies depending on the composition of the bonding liquid, although there is no Limitation of the system, however in the current density domain (eg ' Between mA/cm2 and less than 1〇-兮 and 屯 屯 ( ( (for example, more than 1〇mA/cm2 to 2〇〇mA/cm2 or less), both of them can be finely crystallized_Unshaped hybrid gold alloy A plating film may be used. Further, an insoluble anode such as platinum may be used on the anode. Further, nickel and/or cobalt may be used as the anode. On the other hand, as a mineralizer, for example, it It may be a metal material such as copper or nickel used for electric wiring or the like. Such a metal material may be a base layer formed on a metal substrate or a non-metal substrate, and although not 10/ 22 201111560 It is possible to use either or not, but it is preferable to carry out the bonding under the mixing; in addition, it is also possible to apply a current by using a pulse current. Hereinafter, the present invention will be specifically described by way of examples and comparative examples. The invention is not limited to the following examples. In the examples, the methods and conditions for each analysis and measurement are as follows. [Crystallinity, crystal grain size] RINT2100_ultima+: XRD method manufactured by Rigaku Corporation CuK 〇ί (40 kV/4〇niA) or HF-2200 manufactured by Hitachi High-Tech Co., Ltd.: TEM and THEED method 'Acceleration voltage 200V bright field image [volume fraction] Using HF-2200 manufactured by Hitachi High-Technologies Co., Ltd.: TEM method and THEED method, accelerating voltage 200V bright field image [metal composition] using SEA5100 manufactured by SII Technology Co., Ltd.: EDXRF method [measurement of non-metallic elements] EMI-920V manufactured by Horiba, Ltd., TC-436 (Knoop hardness) manufactured by LECO, USA JISZ2251, the measurement: the load of the 5 gf load holding time of 30 seconds was measured for the 30/zm thick plating film formed on the copper plate. [Specific resistance] K-705RS manufactured by Kyowa Ryokan Co., Ltd.: measured based on JIS K7194 ( Four-probe method) soil [Example 1] ^

L Use an electrical ore solution containing KAu (CN) 2 0.035 mol/dm3, NiS04 · 6h2〇11/22 201111560 〇_〇76 mol/dm3, triammonium citrate 21 _ sulfuric acid to adjust the pH to 6. ^Production = Κ0Η and density lOmA/cm2 in a purity of 99.96 ° /. The current is non-shaped, mixed with gold alloys, thick 丨 _). Crystallization _ Use titanium to cover the titanium electrode (mesh); The bath in the side was subjected to a fine crystal _ amorphous carbon alloy plating film obtained by XRD, TEM, and TH analysis. The XRD song will be the ship's new job D_ in the first: ^^曲^2, degree (four) has fine crystal or undetermined; some, +値 amplitude of more than 1 degree wide peak. In the tem of the tem, it is the result of the mixture of the irregular structure of the crystallization of the crystal. Furthermore, it can be observed on the THEED diagram that the crystal film is unique and the hollow ring of the amorphous shape is mixed. 4 The results show that the obtained plating film has a fine crystal-deformed hybrid structure: 'As a result of observing the TEM photograph, it is found that the average grain edge of the fine crystal is 10 nm, and the volume fraction of the fine crystal phase is a view. On the other hand, composition analysis, Knoop hardness and specific resistance of the obtained fine crystal_unshaped mixed gold alloy plating film were carried out. The detected content ratio: the metal element portion is 41.2 atom% of gold 'nickel is 46.0 atom%; the non-metal element portion. carbon is 138 atom%. The Knoop hardness is; the specific resistance is 89// Ω · cm. [Example 2] In addition to the addition of η-propanol 2〇V〇LQ/. The recording was carried out in the same manner as in Example i, and X RD, tem, and ΤΗΕΕΓ) were analyzed for the obtained mineral film. The XRD curve is shown in Fig. 1, and the TEM image 12/22 201111560 is not shown in Figs. 5 to 7. It can be confirmed that in the XRD curve, there is a wide peak in the vicinity of the peak and half width of the fine crystal or amorphous. Also, in the photo, it can be observed: knot ^. In the THEED diagram, it is observed that the crystallized pattern and the non-form-shaped irregular structure are mixed with each other. The diffraction pattern unique to the crystal is known. The mixed shape of the hollow ring unique to the upper shape. As a result, the positive film which can be obtained has a fine crystal_unshaped hybrid structure. The result of the UEM photograph showed that the average particle diameter of the fine crystals was nm, and the volume fraction of the fine crystal phase was 50%. On the other hand, the purchase of crystalline crystallization-non-formed hybrid gold alloy plating film was carried out to determine the composition of 1_x hardness and specific resistance. The detected content ratio is: gold is 4δ1 atom%, and nickel is 381 atom%. Non-metallic cm 兀素"卩. Carbon is 12.8 atoms ° / °. Knoop hardness is Hk348; it is 89// Q electricity than Timo (Example 3) except that the concentration of citric acid is set to 0.143 mol/dm3, the concentration of ammonia is set to j 2 mol/dm, and the current density is 丨mA/cm2 ( The energization time is 5 sec.) and the 沁^A/cW energization time is 5 seconds. The electroless mineralization is carried out in the same way as the electrolysis. The mineralization is performed in the same manner as in the example i, and the obtained XRD, ΊΈΜ and THEED analysis are performed. . The XRD curve is shown in the first! In the figure, the TEM photograph and the THEED graph are shown in Fig. 8~1〇. It is confirmed that there is a broad peak with a peak radius of 1 degree or more unique to the fine crystal or amorphous shape in the vicinity of 2 (four) 0 degrees of the XRD curve. Further, in the TEM photograph 7 t, it was observed that the crystal grains characteristic of crystals and the irregularities unique to the amorphous form were mixed. Furthermore, it can be observed on the THEED chart that the characteristic diffraction pattern of the knot is mixed with the hollow ring unique to the amorphous shape. set. 13/22 201111560 In the case of current clock application, only the crystal phase is obtained at a current density of 1 mA/cm2, and only the amorphous phase is obtained at 10 mA/cm2. As a result, it was found that the plating film obtained by pulse plating had a fine crystal-unshaped hybrid structure. Further, as a result of observing the TEM photograph, it was found that the average crystal grain size of the fine crystals was 10 nm, and the volume fraction of the fine crystal phase was 6 % by weight. On the other hand, the composition of the obtained film is analyzed by composition, hardness, and specific resistance. The detected content rate of the metal element is 474% of gold and 47.0% by atom of the town. Non-metallic element portion: carbon is 5.6 atom%. The hardness of the 曰'曰' is Hk 222, and the specific resistance is 57 # Q · cm. [Example 4] ^ 5 and 疋 hook, ammonia concentration setting]. 2m〇l/dm, f flow density was set to 5 _2 _2 material sample, and the obtained amorphous gold alloy was plated. The temperature of the second ignition (insulation temperature) is 4 〇〇 t, and the heating rate is 1 〇. The enthalpy, 'row annealing treatment, the obtained woven Si; muheed analysis. In the XRD curve, the TEM photo and the THEED icon are recognized by the second brother: in the XRD score ^ ^ A U map. This is a unique peak with a width of 1 degree or more. Also, the order was observed to be: the characteristic knots of the crystals and the appearance of the TEM photographs. In addition, the regular donation of the special and the non-formal special wealth =, to the crystallization of the mixed structure. Further, the results of the average particle diameter of the 颧 铽 礼 礼 礼 礼 礼 ’ ’ ’ ’ 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微 微14/22 201111560

Use KAu (CN)2 0.035 mol/dm3, C0SO4 · 7H2O 0.076 mol/dm3, citric acid Η20 0.1 mol/dm3, ammonia concentration 〇44 mol/dm3 and adjust the pH to 6 with KOH and sulfuric acid. The electroplating solution is formed into a fine crystal-deformed mixed gold alloy ore film (film thickness l#m) at a temperature of 7 TC at a current density of 10 mA/cm 2 on a copper plate having a purity of 99.96%. On the anode, a titanium electrode (mesh) was coated with platinum; the plating bath in the ore was vigorously stirred. The fine crystal-amorphous hybrid gold alloy plating film obtained by XRD, TTEM and THEED analysis. The XRD curve is shown in the figure, and the TEM image and THEED chart are shown in Figures 14 to 16. It can be confirmed that there is a fine crystal or amorphous specific peak half-turn amplitude near 2 6 > = 40 degrees of the XRD curve. Wide and broad peaks of 1 degree or more. In addition, in the TEM photograph, it is observed that the crystal grains unique to the crystal and the irregular structure unique to the irregular shape are observed. Further, on the THEED map, it is observed that the crystal is uniquely wound. a mixture of spots and amorphous hollow rings. The result is It is understood that the obtained plating film has a fine crystal-unshaped hybrid structure. Further, when observing the results of the TEM photograph, it is found that the average particle diameter of the y-number fine crystal is 5 nm, and the volume fraction of the fine crystal phase is 15%. On the other hand, composition analysis and Knoop hardness of the obtained fine crystal-unshaped mixed gold alloy plating film were measured. The detected content ratio: metal element portion was 36.4 atom% of gold, and cobalt was 40.6. Atomic non-metallic element portion: carbon is 23.0 atom%. Knoop hardness is Hk 18 〇. [Comparative Example 1]

The plating was performed in the same manner as in Example 1 except that the concentration of the citric acid was 0.143 mol/dm 3 and the ammonia degree was set to 0.46 mol/dm 3 , and the obtained coating film was subjected to XRD, TEM, and THEED analysis. The XRD 15/22 201111560 graph is not in Fig. 1, and the TEM is shown in Fig. 17~18. Can be exact · household coffee;, 'slices and twisted coffee icon in the r r = indeed ~ · in the XRD curve of 20 = 4 〇 Lu non-formed peaks and widths of more than 1 degree wide and wide peak 乂 can be confirmed in ^ = An irregular structure unique to amorphous, but not the same as the structure of crystal grain boundaries and knots. In addition, the figure can confirm the ring of non-scheduled positions. From this result, it was found that the mineral coating film was a homogeneous amorphous structure having no fine crystals. Further, the obtained plating_composition analysis, hardness, and specific resistance were measured. The measured content ratio: the metal element portion is gold as a material %, 67.5 atom%; the non-metal element portion · carbon is 17 3 atoms. /. . Knoop hard cm degree is Hk 435; specific resistance is 251 μ Ω [Comparative Example 2] The use of KAu (CN) 2 0.04 mol / dm 3 , NiS04 · 6H20 〇 · 〇 085 mo 〖 / dm3, citric acid · h2 〇. 5 m〇1/dm3, '〇h 〇2.7 mol/dm3 and adjusted to pH 3.5 by electroless plating with sulfuric acid at a temperature of 30 ° C at a current density of 1 〇 mA / cm 2 in purity A hard gold plating film (film thickness 1/zm) was formed on 99%% of the copper plate. Further, a titanium-coated titanium electrode (mesh) was used on the anode; the plating bath in the plating was slowly stirred. Hard gold plating film obtained by XRD, TEM and THEED analysis. The XRD plot is not shown in Figure 1. It is confirmed that there is a sharp peak derived from Au (111) in the vicinity of 2 Θ = 38 degrees of the XRD curve. Further, crystals were confirmed from the TEM photograph and the THEED map. From this result, it was found that the obtained mineral coating film did not have a polycrystalline structure of an amorphous phase. Further, from the results calculated from the XRJD graph, it was found that the average particle diameter of the crystal was u nm. On the other hand, the composition analysis of the obtained plating film was measured, and Nup Hard 16/22 201111560 degrees and ritual. The detected content ratio: the metal element portion is gold of 96.5 atoms/. Nickel is 7777 atom%; non-metal element part: carbon is u atom%. The Knoop hardness is Hkl6〇; the specific resistance is 17; ^.cm. Further, 2θ=50 of the XRD curve shown in Fig. 1 . The sharp peaks seen nearby are caused by the steel of the substrate. In addition, it is 'relative to the degree that the Knoop hardness of the non-added hard gold (AFHG), nickel hard gold (NiHG), and c〇HG which are considered to be high hardness in the Admiralty film is still less than 200. The Knoop hardness of the fine crystal-non-shaped mixed gold alloy plating film of Example 1 has a hardness of 2 to 3 Å equivalent to those of the Knoop. 17/22 201111560 < ί吞势-' io.o inch 0.0 ·0 ·0

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Zirconium €-11Hs If/fpf 〇K. Window_# ^£s §9 .osoo qII9 .os!N ~(δ) ny>I dss ss^ 0 03 1N nv^4- nil®,- $ 18/22 201111560 [Simple description of the diagram] The first figure shows the fine crystal-unshaped hybrid gold alloy plating film obtained in the real 2, 3, 4, and 5, and the gold alloy ore obtained in the comparative example 2, 2 A diagram of the XRD plot of the film. Fig. 2 is a view showing a TEM photograph (100,000 times) of the fine crystal_unshaped mixed gold alloy plating film obtained in Example 1. v Fig. 3 is a diagram showing a TEM photograph (100,000 times) of a fine crystal/non-form hybrid gold alloy plating film obtained in Example 。.乂 Fig. 4 is a view showing the THEED chart of the fine crystal/non-shaped hybrid gold alloy plating film obtained in the example. Fig. 5 is a view showing a TEM photograph of 00 million times of the fine crystal-non-shaped hybrid gold alloy plating film obtained in Example 2. Fig. 6 is a view showing a TEM photograph (100,000 times) of the fine crystal_non-shaped mixed gold alloy plating film obtained in Example 2. Further, Fig. 7 is a view showing the THEED chart of the fine crystal/non-shaped hybrid gold alloy plating film obtained in Example 2. A TEM photograph (300,000 times) of the fine-junction mixed gold alloy plating film obtained in Example 3 is shown in Fig. 8 . Fig. 9 is a view showing a TEM photograph (100,000 times) of the fine crystal-non-disease gold alloy plating film obtained in Example 3. Fig. 1 is a view showing the THEED chart of the fine crystal-definite hybrid gold alloy plating film obtained in Example 3. Fig. 11 is a view showing a TEM photograph (200,000 times) of a fine crystal-definite hybrid gold alloy plating film obtained in Shimon. Fig. 12 shows a TEM photograph (700,000 times) of the fine crystal-definite hybrid gold alloy plating film that the 宭 宭 你 存 4 4 4 4 。 。 。 。 。 。 。 。 。 。 。 。. 19/22 201111560 Fig. 13 is a view showing the THEED diagram of the fine crystal_unshaped hybrid gold alloy ore film obtained in Example 4. Fig. 14 is a view showing a TEM photograph (400,000 times) of the fine crystal_unshaped mixed gold alloy ore film obtained in Example 5. Fig. 15 is a view showing a TEM photograph (100,000 times) of the fine crystal_unshaped mixed gold alloy plating film obtained in Example 5.乂

Fig. 16 is a view showing the THEED chart of the fine crystal-deformed mixed gold alloy plating film obtained in Example 5. J Fig. 17 is a view showing a TEM photograph (1 million times) of the amorphous gold alloy recording film obtained in Comparative Example 1. Further, Fig. 18 is a view showing the THEED chart of the amorphous gold alloy ore film obtained in Comparative Example 1. , ' [Main component symbol description] 钲 20/22

Claims (1)

201111560 VII. Patent application scope: L A type of plating _, a gold alloy, _, a mixture of shapes. Qiao Tian,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, . The body of the sun and the sun = please specialize _ _ _ statistical New York average particle size of 3 〇 nm or less. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Hk 18〇 or more. The substance described in Item 1 - as described in the patent application scope item i, which is in the form of Au -x-yMxCy (wherein, Au or M % work. Co; CA Shilu. 1 ® work / earth attack, M is Ni and / or original adjustment table " /, u Xie atom%; 1 original gamma full-time full-scale 1 · Wei, the surface for electrical pick-up : Γ formation as in the scope of the patent application... Gold salt, _ Met job _ New plating solution, and including cyanide gold melon I and / or starting salt, wrong agent and 10. If the patent scope of the ninth item Is from citric acid, tartaric acid woven liquid, which is mismatched with sulfonic acid and their sodium salts, unloading,: than 疋 疋 acid, citric acid, amines; and, handsome; ammonia; selected ... 2. 3. 4. 5. 6. 7. 8. 9. 21/22 201111560 11. 12. 13. The electrical ore liquid described in item 利), where the mismatch d is tannic acid The pH adjuster is ammonia water. Shen, 5 method: the formation method of gold alloy plating In order to use the electroplating solution described in item 9 of the above-mentioned Γ Γ 81, a gold alloy plating film is formed by subtracting impurities between the crystal phase and the amorphous phase of the object to be plated. It is made of the coated film of the 5th to the 5th.