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WO1983003266A1 - Metaux de chelation - Google Patents

Metaux de chelation Download PDF

Info

Publication number
WO1983003266A1
WO1983003266A1 PCT/US1983/000348 US8300348W WO8303266A1 WO 1983003266 A1 WO1983003266 A1 WO 1983003266A1 US 8300348 W US8300348 W US 8300348W WO 8303266 A1 WO8303266 A1 WO 8303266A1
Authority
WO
WIPO (PCT)
Prior art keywords
lead
tin
solution
plating
weight
Prior art date
Application number
PCT/US1983/000348
Other languages
English (en)
Inventor
Metals Chemicals Corporation Gsp
Shepard Drazin
William Peter Van Antwerp
Original Assignee
Gsp Metals Chemicals Corp
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
Application filed by Gsp Metals Chemicals Corp filed Critical Gsp Metals Chemicals Corp
Priority to JP83501514A priority Critical patent/JPS59500475A/ja
Priority to AU15173/83A priority patent/AU1517383A/en
Publication of WO1983003266A1 publication Critical patent/WO1983003266A1/fr

Links

Classifications

    • 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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • 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
    • C25D3/34—Electroplating: Baths therefor from solutions of lead
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3473—Plating of solder

Definitions

  • This invention relates to electroplating metal elements.
  • microelectronic devices there are semi-conductor components with integrated circuits formed on a substrate, often of leaded glass.
  • the circuits or chips, as they are often called, have metallic elements, terminals or leads, which leave the integrated circuit for connection to other circuitry.
  • These terminals are conventionally formed as spaced parallel fingers and have in the past been plated with pure tin to a thickness of about 200 to 300 micro inches.
  • the plating has included as a co-deposit a brightner such as Janus Green, or a product 6487-Igepal from Dow Chemicals, or Schlotter Tin, a product available through Learonal Corporation in the United States.
  • These organic brightners provide a uniform flow- ability to the tin and also provide a better brighter cosmetic finish. As such these terminals permit the soldering of very fine wires. Without such brightners the appearance of the terminals will be matt-like and the performance of the terminals in so far as the uniform flowability will be reduced.
  • OMP introduced higher specifications for the components to be applied in military applications. This requires that the plating no longer includes the organic brightners of the kind mentioned.
  • the specifications do call for a product having sufficient metal flow of the terminals that solderability and corrosion resistance requirements are achieved.
  • the product should also has the cosmetic brightness characteristics of known products having brighteners.
  • the specification calls for the tin plate to be between 200 to 800 micro inches
  • One method to apply a tin-lead composition to the terminals is to dip a tinned terminal after electroplating into a hot solder dip of tin and lead mixture so as to obtain an eutectic coating on the terminals.
  • a disadvan ⁇ tage with this approach is that the hot dip tends to break the glass substrate as a result of the sudden temperature change.
  • a possible solution is the co-deposit of tfn and lead during electroplating.
  • tin-lead plating as a co-deposit is used as an alternative to tin plating the Government specifications require that the lead proportion shall be 2% to 50% by weight and it should be homogenously co-deposited.
  • electroplating with tin and lead in a chloride or borate solution is not feasible because chlorides and borates attack leaded glass. Further lead is not soluble in a sulfate plating solution.
  • the present invention is directed to a method that satisfies this need.
  • a metallic element is electroplated with lead and tin simultaneously by forming an aqueous plating solution that comprises water, sulfate ion, tin, and chelated lead.
  • the tin is present in an amount effective for electroplating, and in an amount of at least 0.1 ounce as tin sulfate per gallon of water.
  • the lead is present in an amount of at least about 2 parts by weight per 100 parts by weight tin.
  • the element to be plated is placed in this plating solution, and an electrical current is passed through this solution to deposit lead and tin on the metallic element.
  • a plating comprising at least 90% by weight tin and at least 2% by weight lead can be formed.
  • the lead is solublized in the sulfate solution by use of a chelating agent that is bifunctional and is capable of forming with lead a five or six member group that is soluble in a sulfate solution.
  • the chelating agent can be an organo-oxyanion compound.
  • the plating solution and the plated substrate pro- quizd by the method of the present invention are also novel.
  • the plated substrate can include a plating com ⁇ prising co-deposited tin and lead, and preferably consists essentially of tin and lead, containing essentially no brighteners.
  • the present invention can result in an inte ⁇ grated circuit that has a leaded glass component, where the leads or terminals of the circuit are coated with a plating composition that avoids dendrite growth, that can be soldered, and is corrosion resistant.
  • the organo-oxy-anion chelating agent can be an organic acid of molecular weight less than 250 grams/mole, preferably, a gluconic acid, substituted gluconate or alkylacetonates.
  • the terminals are metallic elements, typically made of Kovac. TM (Alloy 42) which are to be plated such that there is a plating comprising a co-deposit of tin and lead.
  • the metallic element can be made of any electrically conductive metal or alloy. This co-deposit should be in the range of at least 50% tin and no more than about 50% lead, and preferably at least 95% tin and no more than 5% lead. In a preferred embodiment the plating has about 98% by weight tin and about 2% by weight lead.
  • the coating consists essen ⁇ tially of tin and lead and contains essentially no bright- eners.
  • the lead is normally insoluble in an aqueous sulfate solution which is constituted by a solution of sulfuric acid as the electrolyte in an electroplating system, the lead is chelated to ensure a sufficiently soluble solution whereby the lead can co-deposit on the metallic element to be plated.
  • the anode would be constituted by an allotrop of tin which in solution becomes stannic tin and stannous tin, and the metallic element to be plated constitutes the cathode.
  • the tin from the anodes passes to deposit on the cathode eleent.
  • the chelated lead is preferably added to the sulfate solution as a liquid of desired concentration, or as a solid wherein complexing has been effected to a chelating agent, preferably an organo-oxy-anionic chelating agent to render the lead complex soluble in the aqueous sulfate bath.
  • a chelating agent preferably an organo-oxy-anionic chelating agent to render the lead complex soluble in the aqueous sulfate bath.
  • the organo-oxy-anionic chelating agent can be selected from the group of glycines, carboxylic acids and alkylacetonates having a molecular weight of less than 250 grams/mole.
  • the plating solution contains water, sulfuric acid, a wetting agent, tin, and chelated lead.
  • sulfuric acid is present in amount of 10% by volume based on the volume of the sulfuric acid and water.
  • the wetting agent is used to assure that an even deposit of plating occurs on the metallic element.
  • a suitable wetting element is Triton X-100 available from Triton X-100.
  • Rohm & Haas in an amount of about 2 grams per gallon of water.
  • the tin can be provided as stannous sulfate in an amount of at least about 0.1 ounce (weight), and typically from about 2 to about 4 ounces (weight) per gallon of water.
  • the amount of chelated lead used depends upon the composition of the plating desired. For the plating to contain at least about 95% tin and from about 2 to about
  • the plating solution contains chelated lead in an amount sufficient to yield at least 2 parts by weight, and preferably from about 5 to about 10 parts by weight per
  • the chelated lead can be prepared according to conventional techniques.
  • the chelating agent is dissolved in water in an amount of 10% by weight chelating agent.
  • lead nitrate is added to the water with a palladium or platinum charcoal catalyst, the mixture is heated to about 65° C, to yield the chelated lead plus excess chelating agent, which is present in more than stoichiometric quantity.
  • the chelated lead is extracted from this mixture at about 40° C with an ethanol/ methanol mixture, about 95 pbw ethanol and about 5 pbw methanol. The solvent is evaporated to yield a solid lead chelate, which can be directly added to the plating solution, or first dissolved in water.
  • the proportions of the elements are as follows: In an electrolyte being one U.S. gallon (4 liters), the sulfuric acid constitutes 10% by weight, and the water 90% by weight. To this in solution there are added about four ounces (120 grams) of tin sulfate. A lead chelated with diethylglycine or EDTA is added to the solution in an amount of half to one ounce (20 grams) so as to constitute about 16% of the solution. In this lead complex about half is lead metal thereby constituting about 5% of the metal relative to the tin metal content.
  • an effective co-deposit of 5% tin and 95% lead is achieved on the metallic element at the cathode.
  • the current applied is in the order of from 1 to 10 amps per square foot of substrate being plated. For high speed plating, 500 amps or higher per square foot can be used. It takes about 10 to about 40 minutes to plate a substrate with a thickness of about 200 micro-inches.
  • the chelating agent is bifunctional, i.e., has at least two chelating groups, either two acid groups, an acid and a base group, or two base groups.
  • Suitable chelating agents for the lead are bifunctional chelating agents capable of forming a five of six member ring with the lead and being capable of solublizing lead in a sulfate solution. Exemplary of the chelating agents that
  • MP have been found successful are gluconic acid, EDTA, diethyl glycine, triethylphosphine, ethylene diamine.
  • the complex between lead ions and the complexing agent produces sufficiently soluble in the sulfate solu ⁇ tion to permit effective electroplating of the lead on the substrate.
  • life cycling at a temperature of 200° F for over 48 hours shows a highly utile product which has superior soldering capabilities and an acceptable appearance. Dendrite and whisker growth has not occured.
  • the plated element satisfies MIL Spec 3.5.6.2.
  • the invention has been described with reference to terminals for microelectronic circuitry, the invention also has application to other products which require plating.
  • the relative amounts of metal being co-deposited can be changed.
  • the amount of lead complex agent present can be adjusted between different percentages to provide co-deposits between 50% lead and 50% tin on the other hand.
  • the chelating agent provides an organo- oxy-anion for oxygen bonding, such as substituted glycines such as dimethylglycine (DMG) , dibutylglycine (DBG).
  • suitable acids besides gluconic acid there are acetic acid and ascorbic acid.
  • Suitable alkylacetonates that are commercially available include for example ethylene acetate, diethylene acetate, and the like.
  • organo-oxy-anion complexing agent instead of an organo-oxy-anion complexing agent, there can be achieved suitable metal complexing with selected organo-hetero-anionic complexing agents. This means that the metal ions are bonded with the anions of nitrogens, or oxygen, sulfur, or phosphorous. Individ ⁇ ually such anions would be nitronium, oxonium, sulfoniu , and phosphonium.
  • Nitrogen complexing with lead can be effected, for example, by ethylene diamine.
  • Sulfur complexing can be effected with thio acids.
  • Phosphorous complexing can be with trialkylphos- phides.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

La chélation d'un métal tel que le plomb dans un électrolyte de sulfate aqueux permet d'obtenir la co-sédimentation du plomb avec de l'étain sur un substrat comprenant un élément métallique. La chélation est effectuée en formant un composé avec un agent de coordination. Les bornes électriques ainsi plaquées ne sont pas atteintes par des excroissances dendritiques. La chélation est effectuée par des agents bifonctionnels de coordination pouvant former un anneau à 5 ou 6 éléments avec le plomb.
PCT/US1983/000348 1982-03-15 1983-03-15 Metaux de chelation WO1983003266A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP83501514A JPS59500475A (ja) 1982-03-15 1983-03-15 キレ−ト化金属
AU15173/83A AU1517383A (en) 1982-03-15 1983-03-15 Chelating metals

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35790782A 1982-03-15 1982-03-15
US357,907820315 1982-03-15

Publications (1)

Publication Number Publication Date
WO1983003266A1 true WO1983003266A1 (fr) 1983-09-29

Family

ID=23407518

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1983/000348 WO1983003266A1 (fr) 1982-03-15 1983-03-15 Metaux de chelation

Country Status (5)

Country Link
EP (1) EP0103638A1 (fr)
JP (1) JPS59500475A (fr)
KR (1) KR840004185A (fr)
AU (1) AU1517383A (fr)
WO (1) WO1983003266A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180804A1 (fr) * 1984-11-07 1986-05-14 Dr.Ing. Max Schlötter GmbH & Co. KG Procédé pour maintenir la soudabilité de revêtements en plomb-étain ainsi que plaquette à circuit imprimé à trous métallisés
GB2351503A (en) * 1999-05-07 2001-01-03 Enthone Omi Zinc/manganese alloy plating bath; passivating
US6387229B1 (en) 1999-05-07 2002-05-14 Enthone, Inc. Alloy plating
US10329680B2 (en) 2015-03-26 2019-06-25 Mitsubishi Materials Corporation Plating solution using sulfonium salt

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2819180B2 (ja) * 1990-02-22 1998-10-30 信康 土肥 すず―鉛―ビスマス合金めっき浴
WO2016152997A1 (fr) * 2015-03-26 2016-09-29 三菱マテリアル株式会社 Solution de placage utilisant du sel de sulfonium

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2751341A (en) * 1952-06-03 1956-06-19 Gen Motors Corp Electrodeposition of lead and lead alloys
US2831803A (en) * 1955-12-02 1958-04-22 Vandervell Products Ltd Electro-deposition of alloys
US3206698A (en) * 1958-05-23 1965-09-14 Corning Glass Works Electro-mechanical delay line having ferroelectric transducer bonded to solid delay medium
US3625837A (en) * 1969-09-18 1971-12-07 Singer Co Electroplating solder-bump connectors on microcircuits
US3875029A (en) * 1974-02-19 1975-04-01 R O Hull & Company Inc Plating bath for electrodeposition of bright tin and tin-lead alloy
US3956123A (en) * 1974-02-19 1976-05-11 R. O. Hull & Company, Inc. Additive for electrodeposition of bright tin and tin-lead alloy

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2751341A (en) * 1952-06-03 1956-06-19 Gen Motors Corp Electrodeposition of lead and lead alloys
US2831803A (en) * 1955-12-02 1958-04-22 Vandervell Products Ltd Electro-deposition of alloys
US3206698A (en) * 1958-05-23 1965-09-14 Corning Glass Works Electro-mechanical delay line having ferroelectric transducer bonded to solid delay medium
US3625837A (en) * 1969-09-18 1971-12-07 Singer Co Electroplating solder-bump connectors on microcircuits
US3875029A (en) * 1974-02-19 1975-04-01 R O Hull & Company Inc Plating bath for electrodeposition of bright tin and tin-lead alloy
US3956123A (en) * 1974-02-19 1976-05-11 R. O. Hull & Company, Inc. Additive for electrodeposition of bright tin and tin-lead alloy

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180804A1 (fr) * 1984-11-07 1986-05-14 Dr.Ing. Max Schlötter GmbH & Co. KG Procédé pour maintenir la soudabilité de revêtements en plomb-étain ainsi que plaquette à circuit imprimé à trous métallisés
GB2351503A (en) * 1999-05-07 2001-01-03 Enthone Omi Zinc/manganese alloy plating bath; passivating
US6387229B1 (en) 1999-05-07 2002-05-14 Enthone, Inc. Alloy plating
GB2351503B (en) * 1999-05-07 2004-02-25 Enthone Omi Alloy plating
US10329680B2 (en) 2015-03-26 2019-06-25 Mitsubishi Materials Corporation Plating solution using sulfonium salt

Also Published As

Publication number Publication date
AU1517383A (en) 1983-10-24
JPS59500475A (ja) 1984-03-22
KR840004185A (ko) 1984-10-10
EP0103638A1 (fr) 1984-03-28

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