CN102317508A - Crystallite-amorphous mixing au-alloy and plated film, plating liquid and plated film formation method - Google Patents
Crystallite-amorphous mixing au-alloy and plated film, plating liquid and plated film formation method Download PDFInfo
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- CN102317508A CN102317508A CN2010800080735A CN201080008073A CN102317508A CN 102317508 A CN102317508 A CN 102317508A CN 2010800080735 A CN2010800080735 A CN 2010800080735A CN 201080008073 A CN201080008073 A CN 201080008073A CN 102317508 A CN102317508 A CN 102317508A
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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
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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
- 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
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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
- C25D7/00—Electroplating characterised by the article coated
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Abstract
The present invention is intended to obtain electrical specification and the excellent crystallite-amorphous mixing au-alloy plated film of mechanical characteristics.Exist with the certain proportion mixing through crystallite phase and amorphous phase, obtained having simultaneously the rerum natura of the advantage of crystalline texture and non-crystal structure.It is characterized in that the median size of crystallite is below the 30nm, the volume percent of crystallite is 10～90%, and knoop hardness is more than the Hk180, and resistivity is below the 200 μ Ω cm.Good specific electrical resistance value and the chemicalstability of gold itself remains on can practical degree, hardness and wear resistant raising simultaneously, thus can effectively be used as the contact material of electric or electronic unit such as junctor, rly..
Description
Technical field
The present invention relates to effectively to be used as the excellent crystallite-amorphous mixing au-alloy plated film of plated film, electrology characteristic and mechanical characteristics of the terminal of e-machine parts; Can form the electroplate liquid of this crystallite-amorphous mixing au-alloy plated film, and the electro-plating method that has used this electroplate liquid.
Background technology
For the junctor of electric or electronic unit, electromechanical formula miniature relay, printed substrate etc., particularly as the electric contact material that requires the position of high reliability, being widely used now is called as the golden plated film of hard gold plated film.Hard gold plated film has been because Xiang Jinzhong has added cobalt, nickel etc., thereby can not reduce satisfactory electrical conductivity and the chemicalstability of gold itself and improve the hardness of plated film.This hard gold plated film is considered to have golden crystallite, and (20～30nm) accumulative microtextures have obtained to obtaining the necessary minimum hardness of the desired wear resistant of contact material (the about Hk170 of knoop hardness) through this microtexture.
On the other hand, be accompanied by the miniaturized of electronic unit in recent years, it is small that the size of electrical contact also becomes, and the plated film that forms in so small contact also become small-sized, filmization require further to improve hardness in order to obtain high abradability.
And; The meeting of the size of contact is near the size of the crystallite of above-mentioned hard gold plated film in the near future; When on so fine contact, forming aforesaid hard gold plated film; Tail off owing to constitute the absolute number of the crystallite of plated film, can envision the equal weather resistance of situation that can not get and on the contact that is suitable for size now, form the golden plated film of hard.Therefore, the inventor has invented the amorphous au-alloy plated film (for example patent documentation 6～8) that is formed by the homogeneous amorphous phase that does not have microlitic structure.Yet, for good specific electrical resistance and chemicalstability with gold itself maintain can practicality degree the time can improve the such purpose of hardness, also have room for improvement.
The prior art document
Patent documentation
The prior art documentation & info relevant with the present invention is following:
Patent documentation 1: the spy opens clear 60-33382 communique
Patent documentation 2: the spy opens clear 62-290893 communique
Patent documentation 3: specially permit communique No. 3452724
Patent documentation 4: specially permit communique No. 3983207
Patent documentation 5: the spy opens the 2004-300483 communique
Patent documentation 6: the spy opens the 2006-241594 communique
Patent documentation 7: the spy opens the 2007-92157 communique
Patent documentation 8: the spy opens the 2007-169706 communique
Non-patent literature
Patent Document 1: Kawai Hui, "Kim - ni Tsukeru alloy メ boots キ Full Full precipitation structure research," Metal Surface Technology, 1968, Vol.19, No.12, p.487-491
Non-Patent Document 2: Shimizu Yasuo other a man, "electrodeposited Au-Ni Alloys Fine Structure and phase ru Concerning Electron Microscopic research," Metal Surface Technology, 1976, Vol.27, No.1, p.20- 24
Non-Patent Document 3: Toru Watanabe with, "フ ア イ nn nn plastic bag Toray a Te イ ki film rather つ The Structure Built Imperial Technology and Other analytical method," IT Association, February 2002, p? 256-262
Non-Patent Document 4: Seeing Chong, the other two people, "Ni-W alloy coating rather つ ki Full high content of と W film features" Metal Surface Technology, 1988, Vol.39, No.12, p.809 -812
Non-Patent Document 5: Toru Watanabe, "rather つ ki of affiliates Formation of amorphous alloy body", Surface Technology, 1989, Vol.40, No.3, p.21-26
Summary of the invention
The present invention In view of the foregoing carries out; Purpose is to provide the wear resistant that hardness improves when having good electrical conductivity and chemicalstability excellent crystallite-amorphous mixing au-alloy plated film; Can form the electroplate liquid of this crystallite-amorphous mixing au-alloy plated film, and the electro-plating method that has used this electroplate liquid.
Although imagined in the process that the inventor studies to achieve these goals repeatedly for small contact can not reduce hardness plated film the microtexture noncrystalline structure than crystalline structure can good specific electrical resistance and the chemicalstability of gold itself be maintained can be practical degree the time raising hardness and wear resistant; But the mean free path of electronics is shorter than crystalline film; Therefore electroconductibility is low, and plated film ftractures owing to internal stress easily.Study on this basis; Discovery contains gold tricyanide salt, nickel salt and/or the cobalt salt of normality through use; The preferred good electroplate liquid of liquid stabilising property that further contains complexing agent such as organic acid, mineral acid or its salt and ammonia or ammonium ion is electroplated; Obtain crystallite phase and amorphous phase very in surprise and mix the crystallite-amorphous mixing au-alloy plated film that exists and form; And this plated film remains on good specific electrical resistance value and the chemicalstability of gold itself can practical degree, and while hardness has also improved.And then the result who studies has accomplished the present invention.
That is, the present invention provides (1) crystallite-amorphous mixing au-alloy plated film, it is characterized in that, crystallite phase and amorphous phase are mixed existence and formed; (2) the good electroplate liquid of liquid stabilising property is characterized in that, is that benchmark contains 0.0001～0.4mol/dm with the gold
3The gold tricyanide salt of concentration is that benchmark contains 0.001～0.5mol/dm with nickel
3The nickel salt of concentration, and/or be that benchmark contains 0.001～0.5mol/dm with the cobalt
3The cobalt salt of concentration; Preferably further contain 0.001～2.0mol/dm
3Complexing agents such as the organic acid of concentration, mineral acid or its salt, 0.001～5.0mol/dm
3The ammonia of concentration or ammonium ion; And (3) electro-plating method, it is characterized in that, use this electroplate liquid on by the plating thing, to form crystallite-amorphous mixing au-alloy plated film.
For crystallite of the present invention-amorphous mixing au-alloy plated film; Crystallite phase and amorphous phase are mixed existence and are formed; Consequently good specific electrical resistance value and the chemicalstability of gold itself remain on can practicality degree; Simultaneously hardness improves, thus can be effectively the contact material of or electronic unit electric as rly. etc.The situation of the known crystalline film that usually constitutes by crystallite, hardness can increase to a certain limit (the for example situation 4nm position of nickel) when the size of the crystal grain of formation diminished, but crystal grain when further diminishing hardness can descend.Whether gold can be suitable for the example that common theory does not have actual measurement; Realize the present invention of crystallite-amorphous hybrid junctions epitaxial for the first time through gold; Crystallite-amorphous mixing au-alloy plated film has solved such problem fully and electroconductibility is high; Be difficult to ftracture, thereby confirmed to be suitable for fully the small contact material that connects electric or electronic unit such as device and rly. first.
Description of drawings
The figure of the XRD figure case of the au-alloy plated film that obtains in crystallite-amorphous mixing au-alloy plated film that Fig. 1 obtains among the embodiment 1,2,3,4,5 for expression and the comparative example 1,2.
The figure of the TEM image (100,000 times) of crystallite-amorphous mixing au-alloy plated film that Fig. 2 obtains among the embodiment 1 for expression.
The figure of the TEM image (1,000,000 times) of crystallite-amorphous mixing au-alloy plated film that Fig. 3 obtains among the embodiment 1 for expression.
The figure of the THEED pattern of crystallite-amorphous mixing au-alloy plated film that Fig. 4 obtains among the embodiment 1 for expression.
The figure of the TEM image (500,000 times) of crystallite-amorphous mixing au-alloy plated film that Fig. 5 obtains among the embodiment 2 for expression.
The figure of the TEM image (1,000,000 times) of crystallite-amorphous mixing au-alloy plated film that Fig. 6 obtains among the embodiment 2 for expression.
The figure of the THEED pattern of crystallite-amorphous mixing au-alloy plated film that Fig. 7 obtains among the embodiment 2 for expression.
The figure of the TEM image (300,000 times) of crystallite-amorphous mixing au-alloy plated film that Fig. 8 obtains among the embodiment 3 for expression.
The figure of the TEM image (1,000,000 times) of crystallite-amorphous mixing au-alloy plated film that Fig. 9 obtains among the embodiment 3 for expression.
The figure of the THEED pattern of crystallite-amorphous mixing au-alloy plated film that Figure 10 obtains among the embodiment 3 for expression.
The figure of the TEM image (200,000 times) of crystallite-amorphous mixing au-alloy plated film that Figure 11 obtains among the embodiment 4 for expression.
The figure of the TEM image (700,000 times) of crystallite-amorphous mixing au-alloy plated film that Figure 12 obtains among the embodiment 4 for expression.
The figure of the THEED pattern of crystallite-amorphous mixing au-alloy plated film that Figure 13 obtains among the embodiment 4 for expression.
The figure of the TEM image (400,000 times) of crystallite-amorphous mixing au-alloy plated film that Figure 14 obtains among the embodiment 5 for expression.
The figure of the TEM image (1,000,000 times) of crystallite-amorphous mixing au-alloy plated film that Figure 15 obtains among the embodiment 5 for expression.
The figure of the THEED pattern of crystallite-amorphous mixing au-alloy plated film that Figure 16 obtains among the embodiment 5 for expression.
The figure of the TEM image (1,000,000 times) of the amorphous au-alloy plated film that Figure 17 obtains in the comparative example 1 for expression.
The figure of the THEED pattern of the amorphous au-alloy plated film that Figure 18 obtains in the comparative example 1 for expression.
Embodiment
Illustrate in greater detail the present invention below.
Crystallite of the present invention-amorphous mixing au-alloy plated film mixes existence by crystallite phase and amorphous phase and forms.
Crystallite of the present invention-amorphous mixing au-alloy plated film comprises nickel and/or cobalt in gold; Its microtexture is that crystallite phase and amorphous phase are mixed the structure that exists simultaneously; Through these characteristics; Compare with the amorphous au-alloy plated film of pure non-crystal structure and can realize good resistivity value and chemicalstability, and high hardness.Such crystallite phase and amorphous phase are mixed the structure that exists and can be confirmed through X-ray diffraction (XRD) pattern, transmission electron microscope (TEM) image and transmission-type high energy electron ray diffraction (THEED) image.
Crystallite of the present invention-amorphous mixing au-alloy plated film considers that from the angle of keeping high firmness the median size of preferred crystallite is below the 30nm, is in particular below the 20nm, and further be below the 15nm.
In addition; Crystallite of the present invention-amorphous mixing au-alloy plated film considers that from the characteristic (good resistivity value and chemicalstability) of keeping gold itself or the angle that has gold or the unexistent high firmness of au-alloy plated film now the volume percent of preferred crystallite is 10～90%, is in particular 15～60%.
Crystallite-amorphous mixing au-alloy plated film: the knoop hardness Hk180 of hardness and resistivity that can obtain having following excellence according to the present invention is above, particularly Hk220 above, further Hk300 above, especially more than the Hk350, and below the resistivity 200 μ Ω cm, particularly below the 150 μ Ω cm, especially below the 100 μ Ω cm.In addition, crystallite of the present invention-amorphous mixing au-alloy plated film utilizes anneal (the keeping 1 hour) crystallite below 300 ℃ mutually to mix the structure that exists can not change (crystallization promptly taking place, the median size of crystallite and volume percent increase) with amorphous phase.
Crystallite of the present invention-amorphous mixing au-alloy plated film has existing gold or the unexistent high firmness of au-alloy plated film when having excellent resistivity value with chemicalstability, can be effectively electric as electromagnetism shutter, isolating switch, thermostatted, rly., various switch, printed substrate etc. or the conducting contact of the terminal of electronic unit etc. from such characteristic consideration.
Crystallite of the present invention-amorphous mixing au-alloy plated film can be used composition formula: Au
100-x-yM
xC
y(Au or M are staple here, can contain unavoidable impurities, and M is Ni and/or Co, and C is a carbon, 1 atom %≤x≤80 atom %, 1 atom %≤y≤30 atom %) expression.
Crystallite of the present invention-amorphous mixing au-alloy plated film can form through the plating of having used the electroplate liquid that contains gold tricyanide salt, nickel salt and/or cobalt salt.
In this electroplate liquid, comprise gold tricyanide salt, nickel salt and/or cobalt salt, can enumerate potassium auric cyanide, gold sodium cyanide, gold tricyanide lithium etc. particularly as gold tricyanide salt; Can enumerate single nickel salt, nickelous nitrate etc. particularly as nickel salt; Can enumerate rose vitriol, Xiao Suangu etc. particularly as cobalt salt.The gold tricyanide salt concn is that benchmark is 0.0001～0.4mol/dm with the gold in the electroplate liquid
3, be preferably 0.001～0.2mol/dm
3, 0.01～0.1mol/dm more preferably
3Nickel salt concentration is that benchmark is 0.001～0.5mol/dm with nickel
3, be preferably 0.01～0.2mol/dm
3Cobalt salt concentration is that benchmark is 0.001～0.5mol/dm with the cobalt
3, be preferably 0.01～0.2mol/dm
3The ratio of gold in the electroplate liquid and nickel and/or cobalt [(Ni+Co)/Au] is preferably 0.01～300 with molar ratio computing, more preferably 1～30 scope.
In addition, this electroplate liquid preferably also contains complexing agent.Organic acid, mineral acid or its salt can be enumerated as this complexing agent, Hydrocerol A, tartrate, oxysuccinic acid, tetra-sodium, phosphoric acid, thionamic acid and their sodium salt, sylvite, ammonium salt etc. can be enumerated as organic acid, mineral acid or its salt with complexing action and pH shock absorption.The concentration of complexing agent is preferably 0.001～2.0mol/dm in the electroplate liquid
3, 0.01～1.0mol/dm particularly
3, 0.1～0.3mol/dm especially
3The ratio of complexing agent and nickel and/or cobalt in the electroplate liquid [complexing agent/(Ni+Co)] is preferably 0.01～100 with molar ratio computing, more preferably 1～4 scope.
In addition, this electroplate liquid preferably also contains ammonia or ammonium ion.Can enumerate ammonium salt of ammoniacal liquor, ammonium sulfate, complexing agent etc. particularly as ammonia or ammonium ion.The concentration of ammonia or ammonium ion is preferably 0.001～5.0mol/dm in the electroplate liquid
3, 0.01～2.0mol/dm particularly
3The crystalline state of the plated film that the volume percent of the median size of this ammonia and crystallization phases, crystallite (or amorphous) is such, plating bath stable closely related.
The pH of this electroplate liquid is preferably 3～11, and pH5～9 particularly are especially about pH6.The adjusting of pH can be used known in the past pH regulator agent such as ammoniacal liquor, Pottasium Hydroxide.
And then; In this electroplate liquid only otherwise can form with film the film rerum natura (the peak half range value of the volume percent of crystallite and median size, XRD figure case, knoop hardness, resistivity) of plated film and produce big influence, can be as required in order to improve glossiness, prevent to cave in, give electroconductibility, give resiliency, enlarge spendable current density range, promote speed of separating out, improve thermotolerance, to improve purpose such as wellability and contain various additives such as tensio-active agent, solvent (for example open and put down that 7-11476 communique, spy are opened the 2004-76026 communique, the spy opens the 2006-37164 communique) with reference to the spy.
The not special restriction of plating condition, electroplating temperature is 20～95 ℃, 50～90 ℃ are suitable especially.Cathode current density also changes according to the composition of electroplate liquid, and not special restriction is at low current density areas (1mA/cm for example
2More than, not enough 10mA/cm
2) and areas of high current density (for example greater than 10mA/cm
2, 200mA/cm
2Below) two zones can obtain crystallite-amorphous mixing au-alloy plated film.And anode can use insoluble anodes such as platinum.Also can use nickel and/or cobalt as anode.On the other hand, as can be enumerated metallic substance such as the copper that is used for electrical wiring etc., nickel by the plating thing.This metallic substance can form bottom on metal base or non-metallic substrate.In addition, whether stirring is arranged, and it doesn't matter, but preferably under agitation electroplate.And, can also apply electric current through pulsed current.
List embodiment and comparative example below the present invention more specifically is described, but the present invention is not limited to following embodiment.In addition, each analysis, method for measuring and condition are described below among the embodiment.
Crystallinity, crystallization particle diameter
Utilize the motor manufacturing RINT2100-Ultima+ of society of science, xrd method, CuK α (40kV/40mA)
Perhaps utilize the Ha イ テ of Hitachi Network ノ ロ イ ジ one ズ society to make HF-2200, TEM and THEED method, acceleration voltage 200V bright field image
Volume percent
Utilize the Ha イ テ of Hitachi Network ノ ロ イ ジ one ズ society to make HF-2200, TEM method and THEED method, acceleration voltage 200V bright field image
Metal is formed
Utilize エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ one society to make SEA5100, EDXRF method
Non-metallic element is measured
Utilize the hole field to make society of institute and make EMIA-920V, the manufacturing TC-436 of U.S. LECO society
Knoop hardness
Measure based on JIS Z 2251, load 5gf, 30 seconds of load hold-time, the plated film of 30 micron thick that on copper coin, form is measured.
Resistivity
Utilize the republicanism reason to grind society and make K-705RS, measure (four probe method) based on JIS K 7194
Embodiment 1
Use contains 0.035mol/dm
3KAu (CN)
2, 0.076mol/dm
3NiSO
46H
2O, 0.21mol/dm
3Triammonium citrate, and pH is adjusted to 6 electroplate liquid, at 70 ℃ of temperature, current density 10mA/cm through KOH and sulfuric acid
2On the copper coin of purity 99.96%, form crystallite-amorphous mixing au-alloy plated film (thickness 1 μ m) under the condition.Here, use platinum lining titanium electrode (netted) as anode, plating bath high degree of agitation in the electroplating process.
Analyze the crystallite-amorphous mixing au-alloy plated film that obtains through XRD, TEM and THEED.Expression XRD figure case in Fig. 1, expression TEM image and THEED pattern in Fig. 2～4.Near 2 θ=40 degree of XRD figure case, can confirm crystallite or the broad peak more than the distinctive peak of amorphous half range value 1 degree.And, can observe the distinctive erratic composition of the distinctive crystallization striped of crystallization and amorphous at the TEM image and mix situation about existing.And then, can observe distinctive diffraction spot of crystallization and the dizzy situation about existing of mixing of the distinctive ring-type of amorphous at the THEED pattern.Can know that by this result the plated film that obtains has formed crystallite-amorphous mixed structure.In addition, the result who observes the TEM image is that the median size of crystallite is 10nm, and the volume percent of crystallite phase is 50%.On the other hand, the composition of crystallite-amorphous mixing au-alloy plated film of obtaining is analyzed, measured knoop hardness and resistivity.Detect 41.2 atom % gold, 46.0 atom % nickel about metallic element, detect 12.8 atom % carbon about non-metallic element.Knoop hardness is Hk347, and resistivity is 89 μ Ω cm.
Embodiment 2
Except the n-propyl alcohol that adds 20vol%, likewise electroplate with embodiment 1, carry out XRD, TEM and THEED to the plated film that obtains and analyze.Expression XRD figure case in Fig. 1, expression TEM image and THEED pattern in Fig. 5～7.Near 2 θ=40 degree of XRD figure case, can confirm crystallite or the broad peak more than the distinctive peak of amorphous half range value 1 degree.And; The TEM image can observe the distinctive erratic composition of the distinctive crystallization striped of crystallization and amorphous mix situation about existing and then, can observe the distinctive diffraction spot of crystallization at the THEED pattern and can know that by this result the plated film that obtains has formed crystallite-amorphous mixed structure with the dizzy situation of mixing existence of the distinctive ring-type of amorphous.In addition, the result who observes the TEM image is that the median size of crystallite is 10nm, and the volume percent of crystallite phase is 50%.On the other hand, the composition of crystallite-amorphous mixing au-alloy plated film of obtaining is analyzed, measured knoop hardness and resistivity.Detect 48.1 atom % gold, 38.1 atom % nickel about metallic element, detect 13.8 atom % carbon about non-metallic element.Knoop hardness is Hk348, and resistivity is 89 μ Ω cm.
Embodiment 3
Making citric acid concentration is 0.143mol/dm
3, ammonia concentration is 1.2mol/dm
3, with current density 1mA/cm
2(50 seconds conduction time) and 10mA/cm
2(5 seconds conduction time) electroplates incessantly alternately, likewise electroplates with embodiment 1 in addition, carries out XRD, TEM and THEED to the plated film that obtains and analyzes.Expression XRD figure case in Fig. 1, expression TEM image and THEED pattern in Fig. 8～10.Near 2 θ=40 degree of XRD figure case, can confirm crystallite or the broad peak more than the distinctive peak of amorphous half range value 1 degree.And, can observe the distinctive erratic composition of the distinctive crystallization striped of crystallization and amorphous at the TEM image and mix situation about existing.And then, can observe distinctive diffraction spot of crystallization and the dizzy situation about existing of mixing of the distinctive ring-type of amorphous at the THEED pattern.The galvanized situation current density of constant current is 1mA/cm
2Only obtain crystallization phases, be 10mA/cm
2Only obtain amorphous phase.Can know that by this result the plated film that is obtained by pulse plating has formed crystallite-amorphous mixed structure.In addition, the result who observes the TEM image is that the median size of crystallite is 10nm, and the volume percent of crystallite phase is 60%.On the other hand, the composition of crystallite-amorphous mixing au-alloy plated film of obtaining is analyzed, measured knoop hardness and resistivity.Detect 47.4 atom % gold, 47.0 atom % nickel about metallic element, detect 5.6 atom % carbon about non-metallic element.Knoop hardness is Hk222, and resistivity is 57 μ Ω cm.
Embodiment 4
Making citric acid concentration is 0.143mol/dm
3, ammonia concentration is 1.2mol/dm
3, current density is 50mA/cm
2In addition; Likewise electroplate with embodiment 1, the amorphous au-alloy plated film that obtains is carried out anneal under 400 ℃ of annealing temperatures (holding temperature), 10 ℃/minute of heat-up rates, insulation 1 hour, atmospheric atmosphere, carry out XRD, TEM and THEED to the plated film after the anneal and analyze.Expression XRD figure case in Fig. 1, expression TEM image and THEED pattern in Figure 11～13.Near 2 θ=40 degree of XRD figure case, can confirm crystallite or the broad peak more than the distinctive peak of amorphous half range value 1 degree.And, can observe the distinctive erratic composition of the distinctive crystallization striped of crystallization and amorphous at the TEM image and mix situation about existing.And then, can observe distinctive diffraction spot of crystallization and the dizzy situation about existing of mixing of the distinctive ring-type of amorphous at the THEED pattern.Can know that by this result the plated film that obtains has formed crystallite-amorphous mixed structure.In addition, the result who observes the TEM image is that the median size of crystallite is 15nm, and the volume percent of crystallite phase is 60%.
Embodiment 5
Use contains 0.035mol/dm
3KAu (CN)
2, 0.076mol/dm
3CoSO
47H
2O, 0.1mol/dm
3Hydrocerol A H
2O, ammonia concentration is 0.44mol/dm
3, and pH is adjusted to 6 electroplate liquid through KOH and sulfuric acid, at 70 ℃ of temperature, current density 10mA/cm
2On the copper coin of purity 99.96%, form crystallite-amorphous mixing au-alloy plated film (thickness 1 μ m) under the condition.Here, use platinum lining titanium electrode (netted) as anode, plating bath high degree of agitation in the electroplating process.
Analyze the crystallite-amorphous mixing au-alloy plated film that obtains through XRD, TEM and THEED.Expression XRD figure case in Fig. 1, expression TEM image and THEED pattern in Figure 14～16.Near 2 θ=40 degree of XRD figure case, can confirm crystallite or the broad peak more than the distinctive peak of amorphous half range value 1 degree.And, can observe the distinctive erratic composition of the distinctive crystallization striped of crystallization and amorphous at the TEM image and mix situation about existing.And then, can observe distinctive diffraction spot of crystallization and the dizzy situation about existing of mixing of the distinctive ring-type of amorphous at the THEED pattern.Can know that by this result the plated film that obtains has formed crystallite-amorphous mixed structure.In addition, the result who observes the TEM image is that the median size of crystallite is 5nm, and the volume percent of crystallite phase is 15%.On the other hand, the composition of crystallite-amorphous mixing au-alloy plated film of obtaining is analyzed, measured knoop hardness.Detect 36.4 atom % gold, 40.6 atom % cobalts about metallic element, detect 23.0 atom % carbon about non-metallic element.Knoop hardness is Hk180.
[comparative example 1]
Except making citric acid concentration is 0.143mol/dm
3, ammonia concentration is 0.46mol/dm
3In addition, likewise electroplate, carry out XRD, TEM and THEED to the plated film that obtains and analyze with embodiment 1.Expression XRD figure case in Fig. 1, expression TEM image and THEED pattern in Figure 17～18.Near 2 θ=40 degree of XRD figure case, can confirm the broad peak more than the distinctive peak of amorphous half range value 1 degree.And, can confirm the distinctive erratic composition of amorphous at the TEM image, do not confirm crystal particle crystal boundary or the crystallization striped structure of rule like this.And then, can confirm that at the THEED pattern the distinctive ring-type of amorphous is dizzy.Can know that from this result the plated film that obtains has formed the non-crystal structure that does not have the homogeneous of crystallite.In addition, the composition of the plated film that obtains is analyzed, measured knoop hardness and resistivity.Detect 15.2 atom % gold, 67.5 atom % nickel about metallic element, detect 17.3 atom % carbon about non-metallic element.Knoop hardness is Hk435, and resistivity is 251 μ Ω cm.
[comparative example 2]
Use contains 0.04mol/dm
3KAu (CN)
2, 0.0085mol/dm
3NiSO
46H
2O, 0.5mol/dm
3Hydrocerol A H
2O, 0.7mol/dm
3KOH, and pH is adjusted to 3.5 electroplate liquid, at 30 ℃ of temperature, current density 10mA/cm through sulfuric acid
2On the copper coin of purity 99.96%, form crystallite-amorphous mixing au-alloy plated film (thickness 1 μ m) under the condition.Here, use platinum lining titanium electrode (netted) as anode, plating bath stirs lentamente in the electroplating process.
Carrying out XRD, TEM and THEED to the plated film that obtains analyzes.Expression XRD figure case in Fig. 1.Near 2 θ=38 degree of XRD figure case, can confirm to be derived from the sharp peak of Au (111).And, confirm to be crystallization from TEM image and THEED pattern.Can know that from this result the plated film that obtains has formed the polycrystalline structure that does not have amorphous phase.In addition, the result who calculates from the XRD figure case is that the crystalline median size is 13nm.On the other hand, the composition of the plated film that obtains is analyzed, measured knoop hardness and resistivity.Detect 96.5 atom % gold, 0.77 atom % nickel about metallic element, detect 2.7 atom % carbon about non-metallic element.Knoop hardness is Hk160, and resistivity is 17 μ Ω cm.
In addition, near the sharp peak of 2 θ=50 degree, seeing in the XRD figure case shown in Figure 1 is based on the copper of substrate.
Can know in addition and think in knoop hardness and the golden plated film of crystallite-amorphous mixing au-alloy plated film of embodiment 1 that the degree that knoop hardness that the high nothing of hardness is added hard cobalt (AFHG), the hard cobalt of nickel (NiHG), CoHG does not reach Hk200 compares, have 2～3 times the high firmness that is equivalent to them.
Claims (13)
1. plated film, it is the plated film of au-alloy, is mixed by crystallization phases and amorphous phase to exist and form.
2. plated film according to claim 1, wherein the volume percent of crystallization phases is 10～90%.
3. plated film according to claim 1, wherein the median size of crystallization phases is below the 30nm.
4. plated film according to claim 1, wherein near the peak half range value 2 θ in the X-ray diffraction pattern=40 degree is more than 1 degree.
5. according to each described plated film in the claim 1～4, wherein knoop hardness is more than the Hk180.
6. according to each described plated film in the claim 1～5, wherein resistivity is below the 200 μ Ω cm.
7. according to each described plated film in the claim 1～6, wherein said plated film is by composition formula: Au
100- X-yM
xC
yExpression, Au or M are staple here, and M is Ni and/or Co, and C is a carbon, 1 atom %≤x≤80 atom %, 1 atom %≤y≤30 atom %.
8. according to each described plated film in the claim 1～7, wherein said plated film is as electric contact material.
9. electroplate liquid, it is the electroplate liquid that is used to form each described plated film in the claim 1～8, comprises gold tricyanide salt, nickel salt and/or cobalt salt, complexing agent and pH regulator agent.
10. electroplate liquid according to claim 9; Wherein complexing agent be selected from Hydrocerol A, tartrate, oxysuccinic acid, tetra-sodium, phosphoric acid, thionamic acid and their sodium salt, sylvite, the ammonium salt more than a kind or 2 kinds; And the pH regulator agent is ammoniacal liquor or Pottasium Hydroxide.
11. electroplate liquid according to claim 10, wherein complexing agent is a Hydrocerol A, and the pH regulator agent is an ammoniacal liquor.
12. the formation method of au-alloy plated film uses each described electroplate liquid in the claim 9～11 to form the au-alloy plated film that crystallization phases and amorphous phase are mixed existence on by the plating thing.
13. electric or electronic unit has used each described plated film in the claim 1～8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009033632A JP5424666B2 (en) | 2009-02-17 | 2009-02-17 | Fine crystal-amorphous mixed gold alloy and plating film, and plating solution and plating film forming method therefor |
| JP2009-033632 | 2009-02-17 | ||
| PCT/JP2010/052364 WO2010095658A1 (en) | 2009-02-17 | 2010-02-17 | Microcrystalline-to-amorphous gold alloy and plated film, and plating solution for those, and plated film formation method |
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| Publication Number | Publication Date |
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| CN102317508A true CN102317508A (en) | 2012-01-11 |
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| CN2010800080735A Pending CN102317508A (en) | 2009-02-17 | 2010-02-17 | Crystallite-amorphous mixing au-alloy and plated film, plating liquid and plated film formation method |
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| Country | Link |
|---|---|
| US (1) | US20120031764A1 (en) |
| JP (1) | JP5424666B2 (en) |
| KR (1) | KR20110132356A (en) |
| CN (1) | CN102317508A (en) |
| DE (1) | DE112010000791T5 (en) |
| TW (1) | TWI476301B (en) |
| WO (1) | WO2010095658A1 (en) |
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| CN108574161A (en) * | 2017-03-14 | 2018-09-25 | 迪尔金属应用有限公司 | Plug-in connector |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012184468A (en) * | 2011-03-04 | 2012-09-27 | Waseda Univ | Plating film, electronic part, plating liquid, and method for forming plating film |
| JP5896508B2 (en) * | 2011-04-28 | 2016-03-30 | 学校法人早稲田大学 | Electroplating solution for production of plating film having composition and nickel carbide Ni3C as main phase |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000026989A (en) * | 1998-07-10 | 2000-01-25 | Nau Chemical:Kk | Production of gold-tin foil |
| CN1940148A (en) * | 2005-09-30 | 2007-04-04 | 关东化学株式会社 | Plated film of gold-cobalt amorphous alloy, electroplating bath, and method for electroplating |
| JP2007169706A (en) * | 2005-12-21 | 2007-07-05 | Univ Waseda | Electroplating solution and electroplating method for forming amorphous gold-nickel based alloy plated film |
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| JPS6033382A (en) | 1983-08-03 | 1985-02-20 | Nippon Pureeteingu Kk | Electrodeposition of amorphous alloy by pulse electrolysis |
| JPS62290893A (en) | 1986-06-09 | 1987-12-17 | Nippon Mining Co Ltd | Gold-nickel alloy plating solution and plating method |
| JPH0711476A (en) | 1993-06-23 | 1995-01-13 | Kojima Kagaku Yakuhin Kk | Palladium plating solution |
| JP3989795B2 (en) | 2002-08-09 | 2007-10-10 | エヌ・イーケムキャット株式会社 | Electrolytic hard gold plating solution and plating method using the same |
| JP2004300483A (en) | 2003-03-28 | 2004-10-28 | Asahi Kasei Chemicals Corp | Material having structure composed of crystalline substance and amorphous substance |
| JP4614052B2 (en) | 2004-07-27 | 2011-01-19 | 石原薬品株式会社 | Nickel barrel plating method |
| WO2006052866A1 (en) * | 2004-11-05 | 2006-05-18 | Tufts University | Treatment of ceria-based catalysts with oxygen to improve stability thereof in the water-gas shift and selective co oxidation reactions |
| JP4868123B2 (en) | 2005-02-04 | 2012-02-01 | 学校法人早稲田大学 | Gold-nickel amorphous alloy plating film, electroplating solution and electroplating method |
-
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2010
- 2010-02-17 KR KR1020117020623A patent/KR20110132356A/en not_active Application Discontinuation
- 2010-02-17 WO PCT/JP2010/052364 patent/WO2010095658A1/en active Application Filing
- 2010-02-17 CN CN2010800080735A patent/CN102317508A/en active Pending
- 2010-02-17 DE DE112010000791T patent/DE112010000791T5/en not_active Withdrawn
- 2010-02-17 US US13/202,050 patent/US20120031764A1/en not_active Abandoned
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000026989A (en) * | 1998-07-10 | 2000-01-25 | Nau Chemical:Kk | Production of gold-tin foil |
| CN1940148A (en) * | 2005-09-30 | 2007-04-04 | 关东化学株式会社 | Plated film of gold-cobalt amorphous alloy, electroplating bath, and method for electroplating |
| JP2007169706A (en) * | 2005-12-21 | 2007-07-05 | Univ Waseda | Electroplating solution and electroplating method for forming amorphous gold-nickel based alloy plated film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108574161A (en) * | 2017-03-14 | 2018-09-25 | 迪尔金属应用有限公司 | Plug-in connector |
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| DE112010000791T5 (en) | 2012-07-26 |
| KR20110132356A (en) | 2011-12-07 |
| JP2010189685A (en) | 2010-09-02 |
| TW201111560A (en) | 2011-04-01 |
| WO2010095658A1 (en) | 2010-08-26 |
| US20120031764A1 (en) | 2012-02-09 |
| TWI476301B (en) | 2015-03-11 |
| JP5424666B2 (en) | 2014-02-26 |
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Application publication date: 20120111 |