CN1003524B - 无电浸镀金溶液 - Google Patents

无电浸镀金溶液 Download PDF

Info

Publication number
CN1003524B
CN1003524B CN86106675.8A CN86106675A CN1003524B CN 1003524 B CN1003524 B CN 1003524B CN 86106675 A CN86106675 A CN 86106675A CN 1003524 B CN1003524 B CN 1003524B
Authority
CN
China
Prior art keywords
mol
content
plating solution
gold plating
electroless gold
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CN86106675.8A
Other languages
English (en)
Other versions
CN86106675A (zh
Inventor
片尾二郎
宫沢修
横野中
富沢明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP60226738A external-priority patent/JPH0735583B2/ja
Priority claimed from JP61088269A external-priority patent/JP2967106B2/ja
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Publication of CN86106675A publication Critical patent/CN86106675A/zh
Publication of CN1003524B publication Critical patent/CN1003524B/zh
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/4501—Shape
    • H01L2224/45012—Cross-sectional shape
    • H01L2224/45015—Cross-sectional shape being circular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144—Gold (Au) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45147—Copper (Cu) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00011—Not relevant to the scope of the group, the symbol of which is combined with the symbol of this group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01047—Silver [Ag]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12389—All metal or with adjacent metals having variation in thickness
    • Y10T428/12396—Discontinuous surface component
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12528—Semiconductor component
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/1284—W-base component
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12889—Au-base component

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemically Coating (AREA)

Abstract

一种无电浸镀金溶液，其组成包括硫代硫酸根合金（Ｉ）络合物，硫代硫酸盐，硫脲，ｐＨ调节剂和稳定剂。镀液的镀金速率和镀液稳定性可与惯用的含氰离子的镀金溶液媲美。镀液可用较少量的还原剂，此外由于镀液中不含氰离子因此使用上也较安全。

Description

无电浸镀金溶液
本发明涉及一种无电浸镀金（化学镀金，Eleetroless Gold Plating）溶液，更具体地是涉及一种毒性低和长时间内保持稳定的无电浸镀金溶液。
迄今已知的无电浸镀金溶液，如《电镀》（Plating）1970年，57期，914-920页所报导的镀金液中主要含有氰合金（Ⅰ）酸钾，氰化钾反硼氢化合物。应用该镀金液可达到1微米/小时的镀金速率，镀液的稳定性也可以保证。然而由于镀液中含有大量的氰离子，因此镀液的操作安全以及废液排放都有问题。
有关不含氰离子的无电浸镀溶金溶液也有过报导，如美国专利3300328号中报导过一种含有氯化金（Ⅲ）和肼为主要成分的镀金溶液;在日本专利公告56-20353号（1981）中报导了一种含有氯合金（Ⅲ）酸钾和硼氢化合物的镀金溶液。但是由于在上述两种无电浸镀金溶液中，金络合物中的金离子是三价离子，因此比起应用氰合金（Ⅰ）酸钾的镀液来说，其镀液中必需加入大量的还原剂。此外美国专利3300328号所报导的无电浸镀金溶液很不稳定，镀液使用约二小时后会产生沉淀，因而无法继续进行镀金。
本发明的目的是提供一种不含氰离子的无电浸镀金溶液，它只需较少量的还原剂，而其镀金速率和镀液稳定性则可以和惯用的含氰离子的镀金液媲美。
上述目的可通过一种无电浸镀金溶液的应用来实现，该镀金溶液中含有：水，硫代硫酸根合金（Ⅰ）络合物（金络合物），硫代硫酸盐（络合剂），硫脲（还原剂），pH调节剂和稳定剂。
上述无电浸镀金溶液的组成是按照以下根据来进行配制。
首先在惯用的无电浸镀金液中应用大量氰离子的目的是，在镀液呈碱性和使用强还原剂的情况下，通过氰离子形成稳定的金络合物来避免由于金络合物中的金络合离子的分解而产生的沉淀。
然而本发明方法则考虑到，在镀液趋中性和还原剂的还原性削弱的情况下，大量氰离子的应用并非必须，在这种情况下，为获得良好的镀金膜层，必须使金络合离子保持稳定状态，本发明方法提出宜于采用硫代硫酸根作为络合剂以取代氰离子。据此，制备无电浸镀金溶液时，选用硫脲作为还原剂，它在中性水溶液中具有很强还原性;应用硫代硫酸根合金（Ⅰ）络合物如硫代硫酸根合金（Ⅰ）酸钠作为金络合物;应用硫代硫酸盐如硫代硫酸钠作为络合剂，并加入稳定剂。而所制备的镀液经鉴定后结果显示，镀液的镀金速率和镀液稳定性可以与惯用的含有氰离子的镀液媲美，而且镀层良好。此外也可发现，当氯合金（Ⅲ）酸盐〔例如四氯合金（Ⅲ）酸钠〕和硫代硫酸盐（如硫代硫酸钠）的混合物作为金络合物时，三价金离子被还原成一价金离子，而且与使用硫代硫酸根合金（Ⅰ）络合物时的效果一样。根据以上发现，本发明方法所提出的无电浸镀金溶液便可配制成。
本发明的无电浸镀金溶液将进一步详述如下。
硫代硫酸根合金（Ⅰ）络合物中包括金原子作为中心原子，而络合物分子中至少包括一个硫代硫酸根离子。硫代硫酸根合金（Ⅰ）络合物的一个例子是化学式为M〈`;;3`〉〔Au（S〈`;;2`〉O〈`;;3`〉）〈`;;2`〉〕的二（硫代硫酸根）合金（Ⅰ）酸盐，其中M表示金属如钠或钾，宜用碱金属尤其以钠为最好。此外，络合物可在含有卤合金酸盐和硫代硫酸盐混合物的水溶液中形成，而该混合物可作为金的来源物。卤合金酸盐可以是例如一种四氯合金酸盐。卤合金酸盐的分子式是MAuX〈`;;4`〉，其中M表示一种金属如钠或钾，宜用碱金属尤其以钠为最好，X表示卤素原子如氟、氯、溴及碘。硫代硫酸盐可以用例如化学式M〈`;;2`〉S〈`;;2`〉O〈`;;3`〉来表示，其中M表示一种金属例如钠或钾，最好是碱金属。
除了上述金来源物外，本发明的无电浸镀金溶液中还包括还原剂，络合剂，pH调节剂及稳定剂。还原剂是一种在金表面上具有还原作用的化合物，如硫脲。络合剂是能够和金离子键合而形成络合物的化合物，例如上述的硫代硫酸盐。稳定剂用来防止络合剂的分解，例如当硫代硫酸盐用作络合剂时，亚硫酸盐可作为稳定剂，它可用化学式M〈`;;2`〉SO〈`;;3`〉来表示，其中M表示一种金属如钠或钾，宜用碱金属尤其是以钠为最好。pH调节剂是一种能够将起始pH值固定在所需的数值的添加剂，例如可以用盐酸或氢氧化钠。此外，具有优选pH缓冲作用的化合物可以作为pH调节剂添加物，如可加入氯化铵或硼砂（Na〈`;;2`〉B〈`;;4`〉O〈`;;7`〉），而以硼砂为宜。
有关本发明的无电浸镀金溶液的各组分，其组成化合物及其化学式已经加以说明。
下述由（a）至（f）各项说明本发明的无电浸镀金溶液各组分的含量及其限定的准则。
（a）硫代硫酸根合金（Ⅰ）络合物含量可以是0.001-0.2摩尔/升，而以0.006-0.04摩尔/升为宜，尤其是以0.001-0.03摩尔/升最好。如果络合物含量低于0.001摩尔/升，镀金过程难于进行，而如果其含量高过0.2摩尔/升，则镀金液中会产生金沉淀。
（b）如果用卤合金（Ⅲ）酸盐和硫代硫酸盐混合物作为金来源物，卤合金（Ⅲ）酸盐的含量可以是0.001-0.2摩尔/升，而以0.006-0.05摩尔/升为宜，尤其以0.001-0.003摩尔/升为最好。如果卤合金（Ⅲ）酸盐的含量低于0.001摩尔/升，镀金过程难以进行，然而如果其含量高过0.2摩尔/升，镀金液中会产生金的沉淀。硫代硫酸盐的含量可以是0.002-0.4摩尔/升，而以0.02-0.12摩尔/升为宜，尤其以0.03-0.08摩尔/升为最好。如果硫代硫酸盐含量低于0.002摩尔/升，则金易于从镀液中沉淀出来，而若其含量高过0.4摩尔/升，则会产生硫的沉淀。
（c）硫脲含量可以是0.001-1.0摩尔/升，而以0.01-0.5摩尔/升为宜，尤其以0.02-0.3摩尔/升为最好。如果硫脲含量低于0.001摩尔/升，镀金过程难于进行，然而如果硫脲添加量高过1.0摩尔/升则对镀金反应无特别作用。
（d）作为络合剂的硫代硫酸盐含量可以是0.001-0.5摩尔/升，而以0.001-0.4摩尔/升为宜，尤其以0.05-0.1摩尔/升最好。如果硫代硫酸盐含量低于0.001摩尔/升，则金易于从镀液中沉淀出来，而若其含量高过0.5摩尔/升，则硫会沉淀。
（e）亚硫酸钠含量可以是0.01-0.8摩尔/升，而以0.08-0.7摩尔/升为宜，尤其以0.15-0.6摩尔/升为最好。如果亚硫酸钠含量低于0.01摩尔/升，则硫易于从镀液中沉淀出来;而如果其含量高过0.8摩尔/升，则镀金反应难于进行。
（f）氯化铵或硼砂的含量可以是0.09-1.0摩尔/升，而以0.4-1.0摩尔/升为宜，尤其以0.4-0.8摩尔/升为最好。如果氯化铵或硼砂含量低于0.09摩尔/升，则镀金反应一引发后即很快减慢甚至中止;而如果氯化铵或硼砂的添加量高过1.0摩尔/升，则对镀金反应无特别作用。
镀液pH值可以是3.0-11.0而以4.0-10.0为宜，尤其以5.0-9.0为最好。镀液温度可以是60-90℃，而以65-85℃为宜，尤其以70-80℃最好。
附图1表示应用本发明之无电浸镀金溶液时，镀金膜厚度（微米）与镀金时间（小时）之间的关系图。
附图2表示应用本发明的无电浸镀金溶液进行镀金的一个电子元件的透视图。
附图3表示附图2所示电子元件沿A-A线的剖视图。
以下各个实施例将对本发明进一步加以详述。
实施例1
试样制备：取一尺寸为2.5厘米×2.5厘米，厚度为0.3毫米的铜片，先电镀一层2微米厚的镀镍层，然后再电镀1微米厚的镀金层而制成试样。将试样经除油液清洗，稀盐酸液浸洗，再经过清水洗净。试样在氮气流中干燥后称重，再将试样在无电浸镀金液中浸镀二小时，镀液组成如下所述，镀液温度为60℃，用盐酸将镀液的pH值调至4.0。
镀液组成：
硫代硫酸根合金（Ⅰ）酸钠 10.0克/升
硫代硫酸钠 50.0克/升
亚硫酸钠 25.0克/升
氯化铵 10.0克/升
硫脲 15.0克/升
镀金过程中，镀液需用强力搅拌。将试样每隔30分钟取出用称量法测定镀金膜厚度，结果如附图1中曲线1所示。镀金开始后经2小时，镀金膜厚度可达1.2微米。所得金膜镀层无光泽，呈金黄色。镀液中没有发现沉淀物。
实施例2
按实施例1的方法制备试样，将其在镀金溶液中浸镀2小时，该镀金溶液组成收如下所述，镀液温度为80℃，并用盐酸将pH值调至5.0。
四氯合金（Ⅲ）酸钠 10.0克/升
硫代硫酸钠 60.0克/升
亚硫酸钠 25.0克/升
氯化铵 10.0克/升
硫脲 8.0克/升
镀金过程中，镀液需用强力搅拌，按例1所述方法测定镀金膜厚度，结果如附图1曲线2所示。自镀金开始经2小时，镀金膜厚度可达1.8微米。所得镀金膜无光泽，呈金黄色，镀液中没有发现沉淀物。
实例3
按实例1所述方法制备试样，将其在镀金溶液中浸镀2小时，镀液组成如下所述，镀液温度为80℃，并用盐酸将镀液pH值调至5.0。
镀液组成：
四氯合金（Ⅲ）酸钠 10.0克/升
硫代硫酸钠 60.0克/升
亚硫酸钠 12.0克/升
氯化铵 40.0克/升
硫脲 8.0克/升
镀金过程中，镀液需用强力搅拌，按例1所述方法测定镀金膜厚度，结果如图1曲线3所示。自镀金开始经2小时，镀金膜厚度可达1.7微米。所得镀金膜无光泽，呈金黄色，镀液中没有发现沉淀物。
如上所述，按照本发明方法，可以应用不含氰离子的镀液进行连续镀金以镀得厚金镀层。而且本发明方法可有效地保证无电浸镀金的操作安全和便利于废液的处理。尤其是当本发明方法应用于各种电子元件如陶瓷质基片的镀金过程时，镀金过程则可更趋理想。
实施例4
本实例说明应用本发明方法的无电浸镀金溶液将各种电子元件进行镀金的实施过程。
附图2中表示本实施例所应用的铝陶瓷基片7，而图2即为该基片的透视图。在钨质小片接合区域4，钨质线接合区域5及柯（Kovar
Figure 86106675_IMG2
）镍基合金质引线6各导体表面上先进行镀镍（3微米厚），再在镀镍层上用置换镀金法（Displacement Gold Plating）镀金（3微米厚）。再将基片用除油液清洗，稀盐酸浸洗，及清水清净，然后在氮气流中干燥。将基片在本发明方法的无电浸镀金液中浸镀3小时，所用镀液组成如实例3所示。镀金过程中，镀液温度为60℃，pH值为4.0，并用强力搅拌。所得镀金膜层厚度用X射线萤光厚度测量仪进行测定，所测得厚度为1.8微米。
将所制得的20个陶瓷质基片样品进行镀金部位的结合性能测试，测试过程如下所述。
（1）小片接合（Die Bonding）性能
将小片接合区与硅基片在430℃下，于氮气氛中相互连接。所得连接样品经热冲击试验（0℃←→200℃的五个循环，各为10秒钟），其中没有产生硅基片的断离的试样则视为合格。
（2）线接合（Wire Bonding）性能
将直径为25微米的金丝用压焊焊于加热至约150℃的各样品的线接合区，在6克重负载下对丝线施加牵引。其中没有产生丝线断离的试样别视为合格。
（3）焊接性能（Solderability）
将样品引线在空气中加热（460℃）15分钟，再经浸焊处理，其中引线区域内有不少于95%部位被焊料浸润的试样则视为合格。
测试结果表明，所有20个样品全部合格。
实施例5
将印刷线路板的铜质端接线路部分（Terminal parts）及插接线路（Connecting plug parts）部分应用本发明之无电浸镀金溶液进行镀金，镀金方法如实例4所示，可以得到如实例4一样的良好效果。
同样地，当各导体部位经镀镍之后再用实例4所示的方法进行无电浸镀金，也可得到与实例4同样满意的结果。

Claims (9)

1、一种包括金来源物，络合剂和还原剂的无电浸镀金溶液，其特征在于，所述金来源物为硫代硫酸根合金（Ⅰ）络合物，络合剂为硫代硫酸盐，还原剂为硫脲，以及含有水，pH调节剂和亚硫酸盐。
2、按权利要求1的无电浸镀金溶液，其特征在于所述硫代硫酸根合金（Ⅰ）络合物含量为0.001-0.2摩尔/升，所述硫代硫酸盐含量为0.001-0.5摩尔/升，所述硫脲含量为0.001-1.0摩尔/升，所述pH调节剂是硼砂或氯化铵其含量为0.09-1.0摩尔/升，所述稳定剂是亚硫酸钠其含量为0.01-0.8摩尔/升，水含量则使所述溶液总量达1升。
3、按权利要求1的无电浸镀金溶液，其特征在于所述硫代硫酸根合金（Ⅰ）络合物含量为0.006-0.04摩尔/升，硫代硫酸盐含量为0.001-0.4摩尔/升，所述硫脲含量为0.01-0.5摩尔/升，所述pH调节剂是硼砂或氯化铵其含量为0.4-1.0摩尔/升，所述稳定剂为亚硫酸钠其含量为0.08-0.7摩尔/升，而水含量则使所述溶液总量达1升。
4、按权利要求1的无电浸镀金溶液，其特征在于所述硫代硫酸根合金（Ⅰ）络合物含量为0.001-0.03摩尔/升，硫代硫酸盐含量为0.05-0.1摩尔/升，硫脲含量为0.02-0.3摩尔/升，所述pH调节剂是硼砂或氯化铵其含量为0.4-0.8摩尔/升，所述稳定剂为亚硫酸钠其含量为0.15-0.6摩尔/升，而水含量则使所述溶液总量达1升。
5、按权利要求1的无电浸镀金溶液，其特征在于所述硫代硫酸根合金（Ⅰ）络合物为卤合金（Ⅲ）酸盐与硫代硫酸盐的反应产物。
6、按权利要求1的无电浸镀金溶液，其特征在于所述硫酸根合金（Ⅰ）络合物为硫代硫酸根合金（Ⅰ）酸钠，而所述硫代硫酸盐为硫代硫酸钠。
7、按权利要求1的无电浸镀金溶液，其特征在于其中硫代硫酸根合金（Ⅰ）络合物为二硫代硫酸根合金（Ⅰ）酸盐。
8、按权利要求1的无电浸镀金溶液，其特征在于其中溶液的pH值为3.0至11.0。
9、无电浸镀金溶液，用于在金属表面、金属沉积层表面或电子原件的导电材料表面形成镀金层，该无电浸镀金溶液是按照上述权利要求1-8的无电浸镀金溶液。
CN86106675.8A 1985-10-14 1986-10-11 无电浸镀金溶液 Expired CN1003524B (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP60226738A JPH0735583B2 (ja) 1985-10-14 1985-10-14 無電解金めつき液
JP226738/85 1985-10-14
JP61088269A JP2967106B2 (ja) 1986-04-18 1986-04-18 電子部品の製造方法
JP88269/86 1986-04-18

Publications (2)

Publication Number Publication Date
CN86106675A CN86106675A (zh) 1987-05-13
CN1003524B true CN1003524B (zh) 1989-03-08

Family

ID=26429676

Family Applications (1)

Application Number Title Priority Date Filing Date
CN86106675.8A Expired CN1003524B (zh) 1985-10-14 1986-10-11 无电浸镀金溶液

Country Status (5)

Country Link
US (3) US4804559A (zh)
EP (1) EP0219788B1 (zh)
KR (1) KR910006643B1 (zh)
CN (1) CN1003524B (zh)
DE (1) DE3663690D1 (zh)

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5202151A (en) * 1985-10-14 1993-04-13 Hitachi, Ltd. Electroless gold plating solution, method of plating with gold by using the same, and electronic device plated with gold by using the same
US4999054A (en) * 1986-12-19 1991-03-12 Lamerie, N.V. Gold plating solutions, creams and baths
US5258062A (en) * 1989-06-01 1993-11-02 Shinko Electric Industries Co., Ltd. Electroless gold plating solutions
JP2866676B2 (ja) * 1989-09-18 1999-03-08 株式会社日立製作所 無電解金めっき液及びそれを用いた金めっき方法
DE4020795C1 (zh) * 1990-06-28 1991-10-17 Schering Ag Berlin-Bergkamen, 1000 Berlin, De
NL9100241A (nl) * 1991-02-12 1991-08-01 Koninkl Philips Electronics Nv Werkwijze voor de vervaardiging van een halfgeleiderinrichting.
US5320703A (en) * 1991-05-09 1994-06-14 Canon Kabushiki Kaisha Process for forming gold crystal film
US5194295A (en) * 1991-06-21 1993-03-16 General Electric Company Ceramic articles having heat-sealable metallic coatings and method of preparation
US5132185A (en) * 1991-06-21 1992-07-21 General Electric Company Ceramic articles having heat-sealable metallic coatings
EP0573918A1 (en) * 1992-06-05 1993-12-15 Matsushita Electric Industrial Co., Ltd. Composite plating coatings
WO1994012686A1 (en) * 1992-11-25 1994-06-09 Kanto Kagaku Kabushiki Kaisha Electroless gold plating bath
US5803957A (en) * 1993-03-26 1998-09-08 C. Uyemura & Co.,Ltd. Electroless gold plating bath
US5318621A (en) * 1993-08-11 1994-06-07 Applied Electroless Concepts, Inc. Plating rate improvement for electroless silver and gold plating
US5910340A (en) * 1995-10-23 1999-06-08 C. Uyemura & Co., Ltd. Electroless nickel plating solution and method
DE19546325C1 (de) * 1995-12-12 1997-06-05 Benckiser Knapsack Ladenburg Verfahren zum Färben von Keramikoberflächen
US5980935A (en) * 1996-05-15 1999-11-09 Kirpotin; Dmitri Cationic lipids and methods of use therefor
USRE43509E1 (en) * 1996-12-19 2012-07-17 Ibiden Co., Ltd. Printed wiring board and method for manufacturing the same
WO1998044067A1 (en) * 1997-03-31 1998-10-08 Hitachi Chemical Company, Ltd. Circuit connecting material, and structure and method of connecting circuit terminal
US7967943B2 (en) * 1997-03-31 2011-06-28 Hitachi Chemical Company, Ltd. Circuit-connecting material and circuit terminal connected structure and connecting method
JP3697829B2 (ja) * 1997-04-09 2005-09-21 ブラザー工業株式会社 インクジェットヘッドの製造方法
US5935306A (en) * 1998-02-10 1999-08-10 Technic Inc. Electroless gold plating bath
JP3920462B2 (ja) * 1998-07-13 2007-05-30 株式会社大和化成研究所 貴金属を化学的還元析出によって得るための水溶液
US6965165B2 (en) 1998-12-21 2005-11-15 Mou-Shiung Lin Top layers of metal for high performance IC's
US6383269B1 (en) 1999-01-27 2002-05-07 Shipley Company, L.L.C. Electroless gold plating solution and process
US6323128B1 (en) * 1999-05-26 2001-11-27 International Business Machines Corporation Method for forming Co-W-P-Au films
US6136702A (en) * 1999-11-29 2000-10-24 Lucent Technologies Inc. Thin film transistors
JP3494940B2 (ja) * 1999-12-20 2004-02-09 シャープ株式会社 テープキャリア型半導体装置、その製造方法及びそれを用いた液晶モジュール
JP4375702B2 (ja) * 2001-10-25 2009-12-02 ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． めっき組成物
US20030131472A1 (en) * 2002-01-15 2003-07-17 Mitac International Corp. Method of fabricating a multi-layer circuit board assembly
JP2004176171A (ja) * 2002-09-30 2004-06-24 Shinko Electric Ind Co Ltd 非シアン電解金めっき液
KR100953612B1 (ko) * 2003-06-02 2010-04-20 삼성에스디아이 주식회사 생체물질 고정용 기판 및 이의 제조방법
EP1645658A4 (en) * 2003-06-05 2011-08-03 Nippon Mining Co SOLUTION FOR CURRENT GILDING
JP4521228B2 (ja) * 2003-07-28 2010-08-11 正也 市村 光析出による金メッキ法及び金メッキ膜形成装置
US7396394B2 (en) * 2004-11-15 2008-07-08 Nippon Mining & Metals Co., Ltd. Electroless gold plating solution
JP4650456B2 (ja) * 2006-08-25 2011-03-16 日立化成工業株式会社 回路接続材料、これを用いた回路部材の接続構造及びその製造方法
US20080191317A1 (en) * 2007-02-13 2008-08-14 International Business Machines Corporation Self-aligned epitaxial growth of semiconductor nanowires
US8922028B2 (en) * 2007-02-13 2014-12-30 Advanced Semiconductor Engineering, Inc. Semiconductor package
CN102605359A (zh) * 2011-01-25 2012-07-25 台湾上村股份有限公司 化学钯金镀膜结构及其制作方法、铜线或钯铜线接合的钯金镀膜封装结构及其封装工艺
CN105112953A (zh) * 2015-09-17 2015-12-02 深圳市瑞世兴科技有限公司 无氰镀金液
US10098241B2 (en) 2015-10-23 2018-10-09 International Business Machines Corporation Printed circuit board with edge soldering for high-density packages and assemblies
CN107200604A (zh) * 2017-05-10 2017-09-26 北京海光仪器有限公司 镀金石英砂的生产方法
JP7135384B2 (ja) * 2018-03-30 2022-09-13 住友大阪セメント株式会社 光導波路素子
KR102019222B1 (ko) * 2018-12-14 2019-09-06 한국과학기술원 다공성 포르피린 고분자에 흡착된 귀금속 회수를 위한 무전해 도금용 도금액 및 무전해 도금방법
US11297718B2 (en) * 2020-06-30 2022-04-05 Gentherm Gmbh Methods of manufacturing flex circuits with mechanically formed conductive traces

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300328A (en) * 1963-11-12 1967-01-24 Clevite Corp Electroless plating of gold
DE1621352C3 (de) * 1967-02-03 1975-05-28 Schering Ag, 1000 Berlin Und 4619 Bergkamen Stabilisiertes alkalisches Kupferbad zur stromlosen Abscheidung von Kupfer
US3697296A (en) * 1971-03-09 1972-10-10 Du Pont Electroless gold plating bath and process
JPS5350680A (en) * 1976-10-19 1978-05-09 Nec Corp Transfer mask for x-ray exposure and its production
DE2803147C2 (de) * 1978-01-25 1984-03-08 W.C. Heraeus Gmbh, 6450 Hanau Tauchgoldbad
US4288841A (en) * 1979-09-20 1981-09-08 Bell Telephone Laboratories, Incorporated Double cavity semiconductor chip carrier
DD150762B1 (de) * 1980-04-17 1987-05-13 Falk Richter Cyanidfreies bad fuer die stromlose goldabscheidung
US4628149A (en) * 1981-11-30 1986-12-09 Nippon Electric Co., Ltd. Substrate having a pattern of an alloy of gold and a noble and a base metal with the pattern isolated by oxides of the noble and the base metals
US4551747A (en) * 1982-10-05 1985-11-05 Mayo Foundation Leadless chip carrier apparatus providing for a transmission line environment and improved heat dissipation
JPS59151443A (ja) * 1983-02-17 1984-08-29 Fujitsu Ltd 半導体装置
JPS59155950A (ja) * 1983-02-25 1984-09-05 Shinko Electric Ind Co Ltd 半導体装置用セラミックパッケージ
JPH0684546B2 (ja) * 1984-10-26 1994-10-26 京セラ株式会社 電子部品
US4681654A (en) * 1986-05-21 1987-07-21 International Business Machines Corporation Flexible film semiconductor chip carrier
US4707394A (en) * 1986-09-19 1987-11-17 Firan Corporation Method for producing circuit boards with deposited metal patterns and circuit boards produced thereby
US4797508A (en) * 1986-09-19 1989-01-10 Firan Corporation Method for producing circuit boards with deposited metal patterns and circuit boards produced thereby

Also Published As

Publication number Publication date
EP0219788B1 (en) 1989-05-31
KR910006643B1 (ko) 1991-08-29
US4804559A (en) 1989-02-14
KR870004163A (ko) 1987-05-07
DE3663690D1 (en) 1989-07-06
CN86106675A (zh) 1987-05-13
US4880464A (en) 1989-11-14
EP0219788A1 (en) 1987-04-29
US4963974A (en) 1990-10-16

Similar Documents

Publication Publication Date Title
CN1003524B (zh) 无电浸镀金溶液
EP0196232B1 (en) Plating bath and method for electroplating tin and/or lead
JP2004510885A (ja) 金属表面上へ銀を無電解めっきするための浴と方法
US5160422A (en) Bath for immersion plating tin-lead alloys
KR930006123B1 (ko) 무전해 금 도금욕 및 이를 사용하는 방법
CN1004010B (zh) 无氰仿金电镀液
JPS56156749A (en) Chemical copper plating solution
US4581256A (en) Electroless plating composition and method of use
US4474838A (en) Electroless direct deposition of gold on metallized ceramics
JP3148428B2 (ja) 無電解金めっき液
JP3565302B2 (ja) 無電解金めっき方法
CN1003974B (zh) 印刷电路板通孔的镀前预处理方法
JPS57140891A (en) Pretreating solution for silver plating
EP0750549B1 (en) Bismuth coating protection for copper
JPS59500475A (ja) キレ−ト化金属
JPS6143660B2 (zh)
US4586990A (en) Chelating metals
JP3685276B2 (ja) パラジウム・銀合金めっき浴
US20040154929A1 (en) Electroless copper plating of electronic device components
CN115433928B (zh) 一种5g高频线路板用化学镀银药水及化学镀银方法
JPH0527710B2 (zh)
Nobel et al. Cyanide-free plating solutions for monovalent metals
JPS619578A (ja) 化学銅めつき方法
Magee et al. The oscillographic polarography of noble metal complexes
SU1761815A1 (ru) Способ обработки покрытий химически осажденных сплавов никель-бор

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C13 Decision
GR02 Examined patent application
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CX01 Expiry of patent term