USRE34484E - Gold-plated electronic components - Google Patents

Gold-plated electronic components Download PDF

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Publication number
USRE34484E
USRE34484E US07/800,462 US80046291A USRE34484E US RE34484 E USRE34484 E US RE34484E US 80046291 A US80046291 A US 80046291A US RE34484 E USRE34484 E US RE34484E
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United States
Prior art keywords
gold
alloy
plated
plated layer
electronic components
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Expired - Lifetime
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US07/800,462
Inventor
Teruyoshi Nagashima
Akio Takami
Akiyo Kasugai
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Niterra Co Ltd
Original Assignee
NGK Spark Plug Co Ltd
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Filing date
Publication date
Priority claimed from JP53108976A external-priority patent/JPS6013078B2/en
Application filed by NGK Spark Plug Co Ltd filed Critical NGK Spark Plug Co Ltd
Priority to US07/800,462 priority Critical patent/USRE34484E/en
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Publication of USRE34484E publication Critical patent/USRE34484E/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/48Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814Conductive parts
    • H01L21/4846Leads on or in insulating or insulated substrates, e.g. metallisation
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
    • C25D5/12Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60Electroplating characterised by the structure or texture of the layers
    • C25D5/623Porosity of the layers
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/24Reinforcing the conductive pattern
    • H05K3/245Reinforcing conductive patterns made by printing techniques or by other techniques for applying conductive pastes, inks or powders; Reinforcing other conductive patterns by such techniques
    • H05K3/246Reinforcing conductive paste, ink or powder patterns by other methods, e.g. by plating
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12889Au-base component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less

Definitions

  • gold Because of its superior physical properties, gold has been widely used as a plated layer on various electronic components. When gold is used in electronic components composed of metallized ceramics, it exhibits good connecting properties in bonding, brazing, soldering, etc. Since gold is very expensive, it is desired to use it in a layer having the smallest possible thickness. In spite of this strong incentive, it has not been realized for one or more reasons. For example, when the gold-plated layer is made thin, an undercoat of plated Ni or Cu, or the metallized layer diffuses into the gold-plated layer because such an undercoat layer or the metallized layer cannot be made compact, i.e., pore free. On the other hand through pinholes in the gold coating, the undercoat layer is degenerated, and discolored under heat. There are further deteriorations in heat resistance and connecting properties, such as the peeling of a silicon tip, deterioration of bonding, and poor cap attachment of an Au/Sn seal. Thus, despite the high cost, a thick gold-plated layer has been required.
  • the present invention provides an electronic component having a metal surface and a gold-plated layer applied to the metal surface in which a plated layer of an alloy of nickel and cobalt or an alloy containing these metals as essential ingredients is applied to the metal surface as an undercoat for the gold-plated layer; and a process for producing such an electronic component.
  • a metallized layer composed mainly of W was printed on green sheets formed from alumina and a resin.
  • the green sheets were laminated and sintered to produce a standard side-braze type LSI ceramic package.
  • a coating 2 microns in thickness having an Ni/Co ratio varying as shown in the table was formed from a plating bath consisting of a Watt bath as a base and cobalt sulfate as to use it as an undercoat for a gold coating.
  • a gold-plated layer, 1.5 microns thick was formed from a commercially available gold plating bath ("Tempelex 401", a trademark for a product of Tanaka Noble Metals Co., Ltd.).
  • Various properties of the resulting product were evaluated.

Abstract

Gold-plated electronic components are disclosed, as well as a process for producing the same, wherein an alloy of nickel and cobalt or an alloy containing these elements as essential ingredients is used as an undercoat for the gold-plated layer.

Description

This is a continuation of application Ser. No. 72,750, filed Sept. 5, 1979, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to gold-plated electronic components and, more specifically, to electronic components of high quality having a thin gold-plated layer and to a method for their production.
2. Description of the Prior Art
Because of its superior physical properties, gold has been widely used as a plated layer on various electronic components. When gold is used in electronic components composed of metallized ceramics, it exhibits good connecting properties in bonding, brazing, soldering, etc. Since gold is very expensive, it is desired to use it in a layer having the smallest possible thickness. In spite of this strong incentive, it has not been realized for one or more reasons. For example, when the gold-plated layer is made thin, an undercoat of plated Ni or Cu, or the metallized layer diffuses into the gold-plated layer because such an undercoat layer or the metallized layer cannot be made compact, i.e., pore free. On the other hand through pinholes in the gold coating, the undercoat layer is degenerated, and discolored under heat. There are further deteriorations in heat resistance and connecting properties, such as the peeling of a silicon tip, deterioration of bonding, and poor cap attachment of an Au/Sn seal. Thus, despite the high cost, a thick gold-plated layer has been required.
SUMMARY OF THE INVENTION
In view of the state of art, extensive investigations of electronic components having a metal surface which do not undergo deterioration in performance even when overcoated with a thin gold-plated layer have been made. These investigations have led to the discovery that such electronic components can be provided by applying a plating of a special alloy as an undercoat layer for gold plating.
The present invention provides an electronic component having a metal surface and a gold-plated layer applied to the metal surface in which a plated layer of an alloy of nickel and cobalt or an alloy containing these metals as essential ingredients is applied to the metal surface as an undercoat for the gold-plated layer; and a process for producing such an electronic component.
BRIEF DESCRIPTION OF THE DRAWING
The FIGURE is a graph showing variations in the Co/Ni ratio in an alloy coating when it is applied from an alloy plating bath having various Co/Ni ratios.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is concerned with electronic components having a gold-plated layer on a metal surface. There is no particular restriction on the metal surface to which the gold-plated layer can be formed by the present invention. Examples of the metal surface are metals which constitute ordinary electronic components such as copper, iron, and aluminum, and ceramic substrates whose surfaces are metallized with materials composed mainly of tungsten, molybdenum, or mixtures thereof. Gold-plated electronic equipment includes, for example, circuit boards for hybrid IC, IC package boards, LSI packages, boards for LED, microswitches, small switches, and connector plugs. Gold is used for a variety of purposes including the wire bonding, tip attachment and soldering (including sealing) of electronic component parts, the provision of conductors and contacts, and also for rust-proofing of these parts. The present invention is applicable to all of these applications.
The present invention is characterized by applying a plated layer of an alloy of nickel and cobalt or an alloy containing these metals as essential ingredients as an undercoat for the gold-plated layer in these electronic components. The method of applying the alloy plating is not limited. It is formed in a thickness of about 0.1 to 10 microns, preferably about 0.5 to 5 microns, by electroplating, electroless plating, etc. The preferred contents of cobalt in the alloy is from about 2 to 60% by weight, and especially from about 7 to 40% by weight. In most cases the balance of the alloy is nickel. If the cobalt content is less than 2 by weight, the heat resistance and connecting property of the resulting alloy coating are not improved appreciably. On the other hand, if the cobalt content exceeds 55% by weight, solderability becomes inferior, and moreover, this is economically disadvantageous because cobalt is much higher in price than nickel. In electroless plating, when sodium hypophosphite is used as reducing agent, the alloy will be 2 to 60% cobalt, 88 to 30% nickel and the remainder, about 10% phosphorus. When sodium borohydride is used as reducing agent, the alloy will be 2 to 60% cobalt, 95-37% nickel and the remainder, about 3% boron. Hydrazine can also be employed as reducing agent.
The plating conditions for the alloy layer are not limited. In the case of electrolytic plating ordinary Ni plating conditions may be used such as 40° to 60° C. and a current density of 1 A/dm2. In the case of electroless plating, when a hypophosphite group is used as reducing agent, the liquid temperature is 90° to 95° C. When a borohydride is used as reducing agent, liquid temperature is 70° to 80° C.
Preferably, the alloy-plated layer is treated in a non-oxidizing atmosphere, such as nitrogen, ammonia-decomposition gas, or hydrogen gas at a temperature of at least about 700° C. and preferably about 700° to 1000° C. This makes the alloy coating compact i.e., free from pores, and increases adhesion between the plated layer and its substrate.
The present inventors have examined the Co/Ni atomic ratio in the alloy coating prepared from an alloy plating bath having varying Co/Ni atomic ratios, and found that as shown in the FIGURE, cobalt deposits preferentially to nickel. To maintain the Ni/Co atomic ratio in the alloy coating constant, it is necessary to supply Co to the plating bath. A supplemental solution for this purpose should contain Ni and Co in a lower Ni/Co atomic ratio than the Ni/Co atomic ratio of the alloy plating bath. A Co/Ni atomic ratio of 0.01 to 0.3 and preferably 0.03 to 0.15 is suitable for the plating bath, but the ratio may vary outside those ranges. A plated coating of uniform quality can be obtained by performing the plating of the alloy while adding a supplemental solution, Ni and Co can also be supplied from the anode in addition to from the solutions.
After the alloy coating is formed by the above method, gold plating is performed in a known manner. Conventional electronic components have a gold plated layer usually having a thickness of about 2 to 4 microns, although the thickness varies depending upon the uses of the components. In contrast, in the present invention, the same performance can be obtained even when the thickness of the gold coating is decreased by 1 to 2 microns because a plated layer of an alloy of nickel and cobalt or an alloy containing these metals as main ingredients is formed as an undercoat for the gold-plated layer. For example, in a ceramic package for LSI, a gold-plated layer usually having a thickness of about 3 to 4 microns is formed when a nickel plated layer is applied as an undercoat. In contrast, in the present invention, the provision of a gold-plated layer having a thickness of about 1.5 to 2 microns is sufficient. The same performance as in conventional articles can be obtained even when the thickness of the gold coating is reduced. This is presumably because the inclusion of cobalt in the undercoat layer greatly inhibits the diffusion of the elements of the undercoat layer into the gold, for example, the diffusion of nickel to gold, and thus makes it possible to retain the purity of the gold-plated layer.
In spite of the thin gold-plated layer in the electronic equipment in accordance with this invention, good performance is obtained. Accordingly, the cost of production can be maintained low, and the present invention has much practical utility.
The following Examples illustrate the present invention in greater detail. It should be understood that the invention is not limited by these Examples.
EXAMPLE 1
A metallized layer composed mainly of W was printed on green sheets formed from alumina and a resin. The green sheets were laminated and sintered to produce a standard side-braze type LSI ceramic package. A coating 2 microns in thickness having an Ni/Co ratio varying as shown in the table was formed from a plating bath consisting of a Watt bath as a base and cobalt sulfate as to use it as an undercoat for a gold coating. Then, a gold-plated layer, 1.5 microns thick, was formed from a commercially available gold plating bath ("Tempelex 401", a trademark for a product of Tanaka Noble Metals Co., Ltd.). Various properties of the resulting product were evaluated.
Testing Methods
(1) Die Bonding Test
A silicon tip was bonded while it was scribed in N2 gas at 450° C. Those products in which at least 90% of the area around the tip was wetted with an Au/Si eutectic alloy were regarded as acceptable.
(2) Aging Test
A die-bonded sample was allowed to stand in N2 gas at 300° C., and the tip was pushed with a force of 500 g at 0, 15, 30, 50, 75, 150 and 200 hours to determine at which time peeling of the tip occurred. Those products in which the tip did not peel for at least 30 hours were regarded as acceptable.
(3) Lid Seal Test
A 1.0 t Kovar cap (with a gold plated-layer of 2.0 microns in thickness) was sealed in a hydrogen furnace at 300° C. for 6 minutes using a 50μ thick 80Au/20Sn preform. Then, a He leak test was conducted in accordance with MIL-STD 883, 1014, and those products which did not show leakage were regarded as acceptable.
(4) Lead Bending Test
A load as exerted on the lead to perform a bending test in accordance with MIL-STD 883,4004. Those products in which the plated coating was not peeled or cracked were regarded as acceptable.
(5) Solderability Test
A lead was dip-soldered in accordance with MIL-STD 883, 2003 and those products in which at least 95% of the lead was wetted with the solder were regarded as acceptable.
(6) High Temperature Standing Test
Samples were allowed to stand in atmosphere air at 175° C. for 250 hours, and those products which did not develop rust were regarded as acceptable.
For each sample tested 10 runs were made. The number of unacceptable runs out of the 10 in each of the above test (1) to (6) is shown in the following table. As is clearly seen from the table, when cobalt is included in a nickel plated undercoating, the results in each test are improved.
                                  TABLE                                   
__________________________________________________________________________
                   Aging test        Lead Bending                         
                                             Solderability                
                                                     High Temperature     
Co (%)   Die Bonding                                                      
                   Before                                                 
                         After                                            
                             Lid Seal Test                                
                                     Test    Test    Standing Test        
Sample                                                                    
    in N.sub.1                                                            
         Before                                                           
              After                                                       
                   Aging Aging                                            
                             Before                                       
                                 After                                    
                                     Before                               
                                         After                            
                                             Before                       
                                                 After                    
                                                     Before               
                                                          After           
No  Plating                                                               
         Aging.sup.(2)                                                    
              Aging.sup.(2)                                               
                   (hours)                                                
                         (hours)                                          
                             Aging                                        
                                 Aging                                    
                                     Aging                                
                                         Aging                            
                                             Aging                        
                                                 Aging                    
                                                     Aging                
                                                          Aging           
__________________________________________________________________________
1   0    2    4    15    0   1   1   0   0   1   3   2    3               
.sup.   2.sup.(1)                                                         
    0    0    0    30    15  0   0   0   0   0   1   0    1               
3    1.2 1    0    30    15  0   1   0   0   1   1   1    1               
4    2.3 0    0    50    30  0   0   0   0   0   0   0    1               
5    5.2 0    0    75    50  0   0   0   0   0   0   0    1               
6    7.5 0    0    150   50  0   0   0   0   0   0   0    0               
7   10.2 0    0    200   75  0   0   0   0   0   0   0    0               
8   21.3 0    0    >200  150 0   0   0   0   0   0   0    0               
9   30.6 0    0    >200  150 0   0   0   0   0   0   0    0               
10  39.5 0    0    >200  150 0   0   0   1   0   0   0    0               
11  52.4 0    0    >200  150 0   0   3   2   0   0   0    0               
12  58.0 0    0    150   75  0   0   5   5   0   2   0    0               
13  69.3 0    0    150   75  0   0   10  7   0   5   1    2               
14  76.5 1    0    75    50  0   1   10  7   3   5   3    5               
15  83.7 0    0    50    30  1   1   10  10  5   7   4    7               
__________________________________________________________________________
 .sup.(1) Sintered in H.sub.2 atmosphere at 800° C.                
 .sup.(2) Aging was conducted by heating goldplated test pieces in the air
 at 450° C. for 10 minutes to impart an aging effect (i.e., to     
 impart a corroding effect in the process).                               
EXAMPLE 2
Example 1 was repeated except that 5% of Fe was included in an Ni/Co alloy. Substantially the same results as in Example 1 were obtained.
While the invention has been described in detail and with reference to specific embodiment thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (2)

What is claimed is:
1. An electronic component, comprising a member consisting of:
a ceramic board substrate having a metallized surface formed thereon;
a metal alloy layer coated on the substrate, the metal alloy layer consisting essentially of nickel and cobalt, wherein the cobalt is contained in an amount of 7 to 40% by weight, wherein the metal alloy layer is formed in a thickness of 0.5 to 5 microns; and
a gold-plated outer surface layer coated on said metal alloy, said gold-plated outer surface layer forming the outer-most surface of the electronic component, wherein the gold-plated outer surface layer is formed in a thickness of .[.0.5.]. .Iadd.1.5 .Iaddend.to 2 microns.
2. The electronic component of claim 1, wherein the balance of said alloy is nickel.
US07/800,462 1978-09-05 1991-11-29 Gold-plated electronic components Expired - Lifetime USRE34484E (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US07/800,462 USRE34484E (en) 1978-09-05 1991-11-29 Gold-plated electronic components

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP53108976A JPS6013078B2 (en) 1978-09-05 1978-09-05 Gold-plated electronic components and their manufacturing method
JP53-108976 1978-09-05
US7275079A 1979-09-05 1979-09-05
US06/344,158 US4465742A (en) 1978-09-05 1982-01-29 Gold-plated electronic components
US07/800,462 USRE34484E (en) 1978-09-05 1991-11-29 Gold-plated electronic components

Related Parent Applications (2)

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US7275079A Continuation 1978-09-05 1979-09-05
US06/344,158 Reissue US4465742A (en) 1978-09-05 1982-01-29 Gold-plated electronic components

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5679469A (en) * 1994-08-02 1997-10-21 Sumitomo Electric Industries, Ltd. Metallized ceramic substrate having smooth plating layer and method for producing the same
US6248964B1 (en) 1999-03-30 2001-06-19 Bourns, Inc. Thick film on metal encoder element
US6420205B1 (en) 1999-03-24 2002-07-16 Kyocera Corporation Method for producing package for housing photosemiconductor element
US6758387B1 (en) * 1999-10-20 2004-07-06 Senju Metal Industry Co., Ltd. Solder coated material and method for its manufacture

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3691289A (en) * 1970-10-22 1972-09-12 Minnesota Mining & Mfg Packaging of semiconductor devices
US3707358A (en) * 1969-06-27 1972-12-26 Philips Corp Crystal support for a semiconductor crystal
US3708405A (en) * 1969-01-22 1973-01-02 Furukawa Electric Co Ltd Process for continuously producing nickel or nickel-gold coated wires
US3729820A (en) * 1969-03-12 1973-05-01 Hitachi Ltd Method for manufacturing a package of a semiconductor element
US3778576A (en) * 1970-01-29 1973-12-11 Echlin Manuf Corp Tungsten electrical switching contacts
US3963455A (en) * 1973-01-12 1976-06-15 Lea-Ronal, Inc. Electrodeposited gold plating

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3708405A (en) * 1969-01-22 1973-01-02 Furukawa Electric Co Ltd Process for continuously producing nickel or nickel-gold coated wires
US3729820A (en) * 1969-03-12 1973-05-01 Hitachi Ltd Method for manufacturing a package of a semiconductor element
US3707358A (en) * 1969-06-27 1972-12-26 Philips Corp Crystal support for a semiconductor crystal
US3778576A (en) * 1970-01-29 1973-12-11 Echlin Manuf Corp Tungsten electrical switching contacts
US3691289A (en) * 1970-10-22 1972-09-12 Minnesota Mining & Mfg Packaging of semiconductor devices
US3963455A (en) * 1973-01-12 1976-06-15 Lea-Ronal, Inc. Electrodeposited gold plating

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
F. A. Lowenheim, Electroplating, McGraw Hill Book Co., New York, 1978, pp. 416 419. *
F. A. Lowenheim, Electroplating, McGraw-Hill Book Co., New York, 1978, pp. 416-419.

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5679469A (en) * 1994-08-02 1997-10-21 Sumitomo Electric Industries, Ltd. Metallized ceramic substrate having smooth plating layer and method for producing the same
US6420205B1 (en) 1999-03-24 2002-07-16 Kyocera Corporation Method for producing package for housing photosemiconductor element
US6248964B1 (en) 1999-03-30 2001-06-19 Bourns, Inc. Thick film on metal encoder element
US6758387B1 (en) * 1999-10-20 2004-07-06 Senju Metal Industry Co., Ltd. Solder coated material and method for its manufacture

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