US20060237097A1 - Immersion method - Google Patents
Immersion method Download PDFInfo
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- US20060237097A1 US20060237097A1 US11/407,706 US40770606A US2006237097A1 US 20060237097 A1 US20060237097 A1 US 20060237097A1 US 40770606 A US40770606 A US 40770606A US 2006237097 A1 US2006237097 A1 US 2006237097A1
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- Prior art keywords
- tin
- acids
- metals
- metal
- acid
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
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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
- C25D5/48—After-treatment of electroplated surfaces
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- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
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- 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
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- 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
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
- H01L2224/85009—Pre-treatment of the connector or the bonding area
- H01L2224/8501—Cleaning, e.g. oxide removal step, desmearing
- H01L2224/85011—Chemical cleaning, e.g. etching, flux
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- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0789—Aqueous acid solution, e.g. for cleaning or etching
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- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
Definitions
- the present invention is directed to an immersion method and composition for inhibiting corrosion of metals and metal alloys. More specifically, the present invention is directed to an immersion method and composition for inhibiting corrosion of metals and metal alloys using inorganic and organic acids.
- solderability defined as the ability of the surface finish to melt and make a good solder joint to other components without defects that impair the electrical or mechanical connection.
- Soldering is basically an attachment procedure that usually involves three materials: (1) the substrate, (2) the component or other device which is desired to be attached to the substrate, and (3) the soldering material itself.
- the soldering material itself is a tin or tin alloy.
- the substrate or component/device may be made of other metals.
- Co-deposited carbon is determined by the plating chemistry one chooses to use.
- Bright finishes contain higher carbon contents than matte finishes. Matte finishes are normally rougher than bright finishes, and provide an increased surface area which results in the formation of more surface oxides than typically are formed with bright finishes.
- Intermetallic compound formation is a chemical reaction between the tin or tin alloy coating and the substrate. The rate of formation depends on temperature and time as well. Higher temperatures and longer times result in a thicker layer of intermetallic compounds.
- the temperature and the time of subsequent post treatment after plating of a tin or tin alloy deposit are typically dictated by the assembly specifications and existing manufacturing layout and practice.
- the entire package goes through many process steps (i.e., a long period of time for such treatments) which require multiple thermal excursions at temperatures as high as 175° C.
- process steps i.e., a long period of time for such treatments
- more and thicker surface oxide forms, and this in turn reduces the solderability of the tin or tin alloy deposit.
- these additional steps may not be omitted since the final components and assemblies would not be complete. Therefore, it is desirable to find ways to prevent or minimize surface oxide formation on such parts.
- One method of addressing the surface oxide problem is to introduce a conformal coating on the surface of the tin or tin alloy deposits.
- This technology may be summarized in two general categories: one that applies a precious metal coating and the other that applies an organic coating.
- the first category is undesirable for the protection of tin or tin alloy deposits because it introduces an expensive, extra step.
- the second category also is undesirable because it may introduce impurities onto other critical areas of the leadframe or electrical component due to the non-selective nature of the organic coating that is deposited. Such impurities are detrimental to subsequent leadframe and IC assembly process.
- U.S. 2004/0099340 (WO 2004/050959) to Zhang et al. attempts to address the surface oxide problem on metal and metal alloy deposits by incorporating trace amounts of phosphorous in the deposits.
- Zhang et al. allege that incorporating phosphorous into the deposits reduces the formation of surface oxide on the deposits.
- the phosphorous compounds are included in the metal and metal alloy electroplating baths, and are co-deposited with the metal or metal alloy.
- the preferred source of phosphorous is the hypophosphites such as NaH 2 PO 4 .
- a disadvantage of such a method is the inclusion of the hypophosphites in the baths. The more components that are added to a bath, the more likely it is to have undesirable interactions in the bath.
- the hypophosphite may interact with other functional additives, which may compromise the grain size, crystal orientation, ductility, hardness, and conductivity of the deposit.
- compositions are provided composed of one or more phosphoric acids or salts thereof in amounts to inhibit oxide formation on metals and metal alloys, and water.
- the compositions provide a stable grain structure for subsequent soldering. The oxide formation is undesirable since it may cause electrical malfunctions of metal components in electrical devices compromising the performance of the devices. Additionally, the compositions do not contaminate the metals and metal alloys they treat.
- compositions consist of one or more inorganic phosphoric acids or salts thereof and one or more organic phosphoric acids and salts thereof in sufficient amounts to inhibit oxide formation on metals or metal alloys, and water.
- methods include contacting metals or metal alloys with compositions including one or more phosphoric acids or salts thereof to inhibit oxide formation on the metals or metal alloys.
- a method includes depositing one or more metals or metal alloys on a substrate; contacting the one or more metals or metal alloys with a composition including one or more phosphoric acids or salts thereof; and reflowing the one or more metals or metal alloys. The method inhibits the formation of oxide on the metals and metal alloys.
- compositions are composed of one or more phosphoric acids or salts thereof, and water.
- the compositions inhibit corrosion on metals and metal alloys, and provide a stable grain structure on the surface of the metals and metal alloys for subsequent soldering. Such corrosion is in the form of an oxide which forms on the metals and metal alloys. Typically it forms on a surface of the metals and metal alloys and is discernable by a discoloration.
- the compositions do not contaminate the metals and metal alloys when they are applied to the metals and metal alloys.
- phosphoric acids include inorganic phosphoric acids such as phosphoric acid (H 3 PO 4 ), also known as orthophosphoric acid, and polyphosphoric acids.
- Inorganic phosphoric acids may be represented by the formula: H n+2 P n O 3n+1 , where n is an integer of 1 or greater. When n is an integer of 2 or greater, the formula represents a polyphosphoric acid.
- n is an integer such that the polyphosphoric acid has an average molecular weight of 110 to 1,500 atomic weight units.
- Salts of phosphoric acids such as sodium phosphate and potassium phosphate may be used.
- the salts include the dibasic sodium phosphate, tribasic sodium phosphate, dibasic potassium phosphate and tribasic potassium phosphate.
- Salts of the polyphosphoric acids also may be used.
- Mixtures of the inorganic phosphoric acids and their salts also may be included in the compositions. Such acids are commercially available, or may be made according to methods described in the literature.
- the inorganic phosphoric acids and their salts are included in the compositions in amounts to inhibit formation of oxides on metals and metal alloys.
- the inorganic phosphoric acids and their salts may be included in the compositions in amounts of 0.1 gm/L to 1500 gm/L, or such as from 0.5 gm/L to 1000 gm/L, or such as from 1 gm/L to 500 gm/L, or such as from 10 gm/L to 100 gm/L, or such as 20 gm/L to 50 gm/L.
- organic phosphoric acids also may be used.
- organic phosphoric acids and salts thereof may be included in the compositions.
- examples of such phosphoric acids include alkylphosphoric acids such as (C 1 -C 20 )alkyl phosphoric acids, hydroxyalkyldiphosphoric acids and salts thereof, hydroxyalkylenephosphoric acids and salts thereof, hexaalkylenediamino-tetra(alkylene-phosphoric) acids and salts thereof, and aminotris(alkylene-phosphoric) acids and salts thereof, and phosphorocarboxylic acids and salts thereof.
- alkylphosphoric acids such as (C 1 -C 20 )alkyl phosphoric acids, hydroxyalkyldiphosphoric acids and salts thereof, hydroxyalkylenephosphoric acids and salts thereof, hexaalkylenediamino-tetra(alkylene-phosphoric) acids and salts thereof, and aminotris(alkylene-phosphoric) acids and salts thereof
- alkylphosphoric acids examples include n-hexylphosphoric acid, n-tetradecylphosphoric acid, n-octylphosphoric acid, n-decylphosphoric acid, n-dodecylphosphoric acid, n-octadecylphosphoric acid, n-hexadecylphosphoric acid, methane diphosphoric acid, 1,2-ethanediphosphoric acid, and 1,3-proanediphosphoric acid.
- suitable hydroxyalkyldiphosphoric acid are hydroxyethanediphosphoric acid, hydroxymethyl diphosphoric acid and hydroxyethyl diphosphoric acid (HEDP).
- An example of a suitable hydroxyalkylenediamino-tetra(alkylene-phosphoric) acid is hexamethylenediamino-tetra(methylenephosphoric) acid.
- An example of an aminotris(alkylene-phosphoric) acid is aminotris(methylene-phosphoric) acid.
- Examples of phosphorocarboxylic acids include phosphoroacetic acid, 2-phosphoropropionic acid, 2-hydroxy-phosphoroacetic acid, 2-hydroxy-2-methyl phosphoroacetic acid, 2-hydroxy-2-butyl phosphoroacetic acid, 3-phosphoro-3-hydroxy butyric acid, 2-phosphoroethane-1,2-dicarboxylic acid, 2-phosphoro-butane-1,2,4-tricarboxylic acid, 2-amino-phosphoroacetic acid, 2-amino-2-methyl phosphoroacetic acid, and phosphoromethylimino diacetic acid.
- Examples of other suitable organic phosphoric acids include methylamino bis-methylene phosphoric acid, phosphoromethyl glycine, bis-phosphoromethyl glycine, 1-aminoethyl-1,1-diphosphoric acid, hexamethylene diamine tetrakis(methylene phosphoric) acid, diethylene triamine tetra(methylene phosphoric) acid, diethylene triamine penta(methylene phosphoric) acid, bis-hexamethylene triamine pentakis(methylene phosphoric) acid and salts thereof.
- aminotris(methylene-phosphoric) acids are used as the organic phosphoric acid, for example aminotris(methylene-phosphoric) acid. It is commercially available as DEQUEST® 2000 and DEQUEST® 2006 (available from Brenntag, Germany).
- the organic phosphoric acids and their salts are included in the compositions in amounts of 0.005 gm/L to 1 gm/L, or such as from 0.01 gm/L to 0.5 gm/L, or such as from 0.1 gm/L to 0.25 gm/L.
- phosphorous acid H 3 PO 3
- Phosphorous acid may be included in amounts of 0.1 g/L to 1 g/L.
- compositions are aqueous and are applied to metals and metal alloys to inhibit the formation of oxides on the metals and the metal alloys.
- the pH of the compositions is from 1 to 6, or such as from 2 to 4.
- the compositions may be applied on any metal and metal alloy where oxide formation may be inhibited. Examples of such metals include tin, copper, nickel, silver and alloys thereof.
- the compositions are used to inhibit oxide formation on tin and its alloys.
- tin alloys include tin/lead, tin/copper, tin/silver, tin/silver/copper, tin/nickel, tin/bismuth and tin/gold. More typically they are used to inhibit oxide formation on tin and tin/lead. Most typically they are used to inhibit oxide formation on tin.
- compositions may be applied to the metals and metal alloys at any period after the metals and metal alloys are deposited on a substrate. Typically they are applied right after the metal or metal alloy plating as a post-treatment process.
- the oxidation inhibiting action of the compositions may last days after the post-treatment and still be effective when the metal or metal alloy is reflowed. Accordingly, the treated metal or metal alloy may be stored or transported and reflowed latter and still inhibit oxidation.
- Tin may form tin oxide (SnO) after reflow. This is noticeable on the deposited tin after the reflow process by a discoloration of the tin surface. The longer the exposure of the reflowed tin to oxygen and the higher the temperature, the more noticeable is the discoloration. Typically the discoloration is observable as a yellow tint on the surface of the tin. In more severe cases of oxidation, the tin may appear brown and even purple after reflow. Oxidation of the tin may result in poor electrical conduction or shorts in electronic devices where the tin is plated such as in printed wiring boards and leadframes.
- SnO tin oxide
- the presence of oxidation on the tin or tin alloy surface compromises any subsequent soldering process of the tin or tin alloy. Poor soldering may result in separation of the soldered parts resulting in malfunction of the electronic device.
- the compositions inhibit the undesirable oxidation, provide a stable grain structure on the surface of the tin, and do not contaminate the tin surface.
- compositions may be applied to the metals and metal alloys by any suitable method in the art.
- the compositions may be sprayed on the metals and metal alloys or the metals and metal alloys may be immersed in the compositions.
- the metals and metal alloys are immersed in the compositions.
- the compositions are at temperatures of 18° C. to 60° C., or such as from 20° C. to 50° C., or such as from 25° C. to 40° C.
- the amount of time the metals and metal alloys are exposed to the oxide inhibiting composition may vary. Typically, the metals and metal alloys are in contact with the compositions for at least 5 sec. before any subsequent processing steps. More typically, the metals and metal alloys are in contact with the composition for 5 sec to 60 sec., or such as from 10 sec. to 30 sec. The metals and metal alloys may then be optionally rinsed with water to remove any excess oxide inhibiting composition.
- a reflow process may follow the treatment and rinse step. Any suitable reflow process may be used. Reflow may be by heating by vapor phase reflow, laser reflow, plasma, oven melting, and passing an electrical current through the metals and metal alloys, or by any other method of heating the metals and metal alloys above their liquidus temperature.
- compositions may be used with any suitable metal deposition process such as electrolytic metal deposition or electroless metal deposition.
- the compositions may be used to inhibit oxidation of metals and metal alloys used in the manufacture of any article which is made with electrolytically or electrolessly deposited metals. Examples of such articles include printed wiring boards, connectors, passive components, bumps on wafers and leadframes
- a substrate such as a printed wiring board, connectors or leadframe, optionally may be cleaned prior to metallization. Any suitable cleaning process may be used which is acceptable in the metallization arts.
- the substrate is ultrasonically cleaned in a suitable solution.
- cleaning solutions may include silicate compounds, alkali metal carbonates and other components such as alkali metal hydroxides, glycol ethers and one or more chelating agents.
- the substrate may be activated with a suitable acid such as a mineral acid.
- a suitable acid such as a mineral acid.
- An example of such an acid is sulfuric acid.
- other mineral acids may be used.
- the acids are used in conventional concentrations well known in the art.
- the substrate may then be plated with a metal such as tin, copper, nickel, silver or an alloy thereof or, for example, tin may be plated on nickel or tin on copper.
- a metal or metal alloy plating bath may be used.
- a typical tin plating bath may include one or more water soluble tin salts such as tin sulfate, tin alkyl sulfonates such as tin sulfonate, tin alkanol sulfonic acid, and tin halides such as tin chloride.
- the bath also includes electrolytes such as sulfuric acid, alkyl sulfonates, alkanol sulfonates and halide salts to provide an electro-conductive matrix.
- electrolytes such as sulfuric acid, alkyl sulfonates, alkanol sulfonates and halide salts to provide an electro-conductive matrix.
- Surfactants also may be included as well as other conventional additives to provide a desirable tin layer.
- the amounts of the components are conventional and are well known in the art and may be obtained from the literature.
- U.S. Pat. No. 5,174,887 and U.S. Pat. No. 5,871,631 disclose suitable tin electroplating baths.
- U.S. Pat. No. 4,880,507 and U.S. Pat. No. 4,994,155 disclose suitable tin/lead plating baths.
- a suitable copper electrolytic bath may include one or more water soluble copper salts such as copper sulfate pentahydrate, a sulfuric acid matrix to provide electrical conduction in the bath, chloride ions from sodium chloride or hydrogen chloride, levelers, carriers, brighteners and other additives such as surfactants to provide the desired copper metal layers.
- water soluble copper salts such as copper sulfate pentahydrate
- sulfuric acid matrix to provide electrical conduction in the bath
- chloride ions from sodium chloride or hydrogen chloride levelers, carriers, brighteners and other additives such as surfactants to provide the desired copper metal layers.
- levelers, carriers, brighteners and other additives such as surfactants to provide the desired copper metal layers.
- a nickel bath may include one or more water soluble nickel salts such as nickel chloride, nickel sulfate hexahydrate, and nickel sulfamate tetrahydrate.
- One or more acids such as boric acid and ascorbic acid may be included.
- one or more conventional additives may be included to provide a desired nickel layer.
- the amounts of the components may be conventional and are well known in the art, or may be obtained from the literature.
- An example of a suitable nickel electroplating solution is disclosed in U.S. Pat. No. 6,858,122.
- the metals may be deposited at any suitable temperature and current density depending on the metal or metal alloy plated.
- the bath temperatures range from 15° C. to 40° C., or such as from 25° C. to 30° C.
- the current density is typically from 1 ASD to 35 ASD, or such as from 5 ASD to 30 ASD, or such as from 10 ASD to 20 ASD.
- any conventional current density used to plate tin, copper, nickel or alloys thereof may be used. Suitable current densities are disclosed in the literature.
- the metals or metal alloys After the metals or metal alloys are deposited on the substrates, they undergo post-metallization treatment with the oxide inhibition compositions as described above. The treated metals or metal alloys may then be reflowed by one of the methods described above. After reflow the metal or metal alloy plated substrate may be further processed as desired.
- each brass connector was removed from the cleaning solution and activated with technical grade sulfuric acid.
- the brass connectors were immersed in a 100 mL/L of the technical grade sulfuric acid at room temperature for 10 sec. Each brass connector was then nickel plated.
- the 12 brass connectors were joined in electrical communication with a rectifier and an insoluble electrode which functioned as an anode.
- the brass connectors functioned as cathodes.
- the anode and the 12 brass connectors were placed in an electrolytic nickel plating solution to complete the circuit.
- the nickel plating solution was an aqueous solution which included 700 mL/L of nickel sulfamate solution (180 g/L) and 8 g/L of nickel chloride concentrate (500 g/L) to provide an electroplating solution containing 115 g/L to 135 g/L of nickel ions.
- the brass connectors were plated with a 1 ⁇ m layer of nickel. Electroplating was done at 55° C. at a current density of 10 ASD for 120 sec. The nickel plated brass connectors were then removed from the nickel electrolytic solution, rinsed with water and then plated with tin.
- Each nickel plated brass connector was then placed in a tin electrolyte solution and joined in electrical communication with a rectifier and an insoluble electrode, which functioned as the anode.
- the nickel plated brass connectors functioned as cathodes.
- the tin electrolyte included 60 gm/L of tin ions from tin methane sulfonate and 150 mL/L of 70% methane sulfonic acid as the matrix. The temperature of the tin bath was 15° C. during tin deposition.
- the current density during tin deposition was 10 ASD. Tin plating was done for 30 sec. and a tin layer of 2 ⁇ m was deposited on the nickel layer of each brass connector. The tin layer appeared smooth and bright.
- a stock solution of an immersion acid oxide inhibitor composition was prepared by mixing 1200 gm of technical grade (85%) phosphoric acid and 100 gm of aminotris(methylene-phosphoric) acid in water to make a one liter aqueous solution. A 20% v/v aqueous immersion acid composition was then made from the stock solution to be used for a tin plating post treatment.
- a control post treatment composition also was prepared. It included 40% sodium hydroxide, 30% sodium carbonate, 20% sodium metasilicate and 10% sodium tripolyphosphate. The solid materials were mixed with sufficient water to make a 10 g/L solution.
- the remaining 3 tin and nickel plated brass connectors which were treated with the immersion acid composition, were placed in the same conduction/convection oven as the first six but were reflowed three times using the temperature profile above and the dwell times. All three were removed from the oven after reflow and allowed to cool to room temperature.
- One of the connectors was free of any visible signs of surface oxidation (0). One showed discoloration (4), and one showed noticeable, but not severe discoloration (2).
- the 3 remaining connectors were immersed in the control treatment solution described above. Each connector remained in the solution for 5 sec. at a temperature of 50° C. After they were removed from the treatment solution, they were rinsed with water and hot air dried at 100° C. One was reflowed once using the oven and temperature profile with dwell times described above. The second was reflowed twice and the third was reflowed three times using the temperature profile and dwell times described above.
- the immersion acid composition containing an inorganic phosphoric acid and an organic phosphoric acid showed improvement in preventing tin oxidation over the controls.
- each brass connector was removed from the cleaning solution and activated with technical grade sulfuric acid.
- the brass connectors were then immersed in a 100 mL/L of the technical grade sulfuric acid at room temperature for 10 sec. Each brass connector was then nickel plated.
- the 16 brass connectors were joined in electrical communication with a rectifier and an insoluble electrode which functioned as an anode.
- the brass connectors functioned as cathodes.
- the anode and the 16 brass connectors were placed in an electrolytic nickel plating solution to complete the circuit.
- the nickel plating solution was an aqueous solution which included 700 mL/L of nickel sulfamate solution (180 g/L) and 8 g/L of nickel chloride concentrate (500 g/L) to provide an electroplating solution containing 115 g/L to 135 g/L of nickel ions.
- the brass connectors were plated with a 1 ⁇ m layer of nickel. Electroplating was done at 55° C. at a current density of 10 ASD for 120 sec. The nickel plated brass connectors were then removed from the nickel electrolytic solution, rinsed with water and then plated with tin.
- Each nickel plated brass connector was then placed in tin electrolyte baths and joined in electrical communication with a rectifier and an insoluble electrode, which functioned as the anode.
- the nickel plated brass connectors functioned as cathodes.
- the tin electrolyte baths included 60 gm/L of tin ions from tin methane sulfonate and 150 mL/L of 70% methane sulfonic acid as the matrix. All sixteen connectors were plated with tin at 15° C.
- a stock solution of an immersion acid oxide inhibitor was prepared by mixing 1200 gm of technical grade (85%) phosphoric acid and 100 gm of aminotris(methylene-phosphoric) acid in water to make a one liter aqueous solution. From the stock solution, dilute solutions of 5% v/v, 10% v/v, 20% v/v and 30% v/v were made to treat the tin and nickel plated brass connectors.
- Each of the diluted immersion oxide inhibiting compositions was used to treat one connector tin plated at 10 ASD and 20° C. and one connector at 15 ASD and 20° C. and another pair at 50° C. Each tin and nickel plated connector was immersed in the compositions for 5 sec. They were then removed and hot air dried at 100° C.
- Each of the treated connectors was then placed in a Sikama FalconTM 8500 conduction/convection oven for reflow of the tin layers.
- the temperature profile was 125° C. to 180° C. to 240° C. to 260° C. to 240° C. and then back down to room temperature.
- the connectors dwelled in each temperature zone for 30 sec. After reflow, the connectors were visibly examined for any tin oxide formation.
- the immersion acid oxide inhibiting compositions inhibit the formation of tin oxide on tin plated substrates after reflow.
Abstract
A composition and method for inhibiting corrosion is disclosed. Metals and metal alloys are treated with compositions which contain inorganic and organic acids that prevent oxide formation on the metals and metal alloys.
Description
- The present invention is directed to an immersion method and composition for inhibiting corrosion of metals and metal alloys. More specifically, the present invention is directed to an immersion method and composition for inhibiting corrosion of metals and metal alloys using inorganic and organic acids.
- Prevention of corrosion of metals and metal alloys is a challenging problem in numerous industries. The corrosion of metal and metal alloys has been especially problematic in the electronic materials industry where corrosion may lead to faulty electrical contact between components in electronic devices. The steel industry has also suffered from the corrosion problem. For example, electroplated tin and tin alloy coatings have been used in electronics and other applications such as wire, and steel strip for many years. In electronics, they have been used as a solderable and corrosion resistive surface for contacts and connectors. They are also used in lead finishes for integrated circuit (“IC”) fabrication. In addition, a thin layer of tin or tin alloy is applied as the final step for passive components such as capacitors and transistors.
- Though applications vary, there are some commonalities regarding the requirements for this final surface finish. One issue is long term solderability, defined as the ability of the surface finish to melt and make a good solder joint to other components without defects that impair the electrical or mechanical connection. Soldering is basically an attachment procedure that usually involves three materials: (1) the substrate, (2) the component or other device which is desired to be attached to the substrate, and (3) the soldering material itself. The soldering material itself is a tin or tin alloy. The substrate or component/device may be made of other metals.
- There are many factors that determine good solderability, the three most important of which are extent of surface oxide formation (corrosion), amount of co-deposited carbon, and extent of intermetallic compound formation. Surface oxide formation is a natural occurring process because it is thermodynamically favorable. The rate of formation of the surface oxide depends on the temperature and time. The higher the temperature and the longer the exposure time, the thicker the surface oxide formed. In electroplated tin or tin alloy coatings or deposits, surface oxide formation also depends on the surface morphology of the coating or deposit. When comparing pure tin to tin alloy coatings, for example, tin alloys generally form less or thinner surface oxides when all other conditions are equal.
- Co-deposited carbon is determined by the plating chemistry one chooses to use. Bright finishes contain higher carbon contents than matte finishes. Matte finishes are normally rougher than bright finishes, and provide an increased surface area which results in the formation of more surface oxides than typically are formed with bright finishes.
- Intermetallic compound formation is a chemical reaction between the tin or tin alloy coating and the substrate. The rate of formation depends on temperature and time as well. Higher temperatures and longer times result in a thicker layer of intermetallic compounds.
- To ensure solderability, it is important to 1) deposit a sufficient layer of tin or tin alloy such that surface oxide or intermetallic compound formation does not consume the entire layer, and 2) to prevent or minimize exposure of the tin plated surface to elevated temperatures for extended periods of time.
- It is relatively easy to achieve 1), but it is difficult to achieve 2). The temperature and the time of subsequent post treatment after plating of a tin or tin alloy deposit are typically dictated by the assembly specifications and existing manufacturing layout and practice. For example, in “two tone” leadframe technology, after the tin or tin alloy plating, the entire package goes through many process steps (i.e., a long period of time for such treatments) which require multiple thermal excursions at temperatures as high as 175° C. Inevitably, more and thicker surface oxide forms, and this in turn reduces the solderability of the tin or tin alloy deposit. In current processing, these additional steps may not be omitted since the final components and assemblies would not be complete. Therefore, it is desirable to find ways to prevent or minimize surface oxide formation on such parts.
- One method of addressing the surface oxide problem is to introduce a conformal coating on the surface of the tin or tin alloy deposits. This technology may be summarized in two general categories: one that applies a precious metal coating and the other that applies an organic coating. The first category is undesirable for the protection of tin or tin alloy deposits because it introduces an expensive, extra step. The second category also is undesirable because it may introduce impurities onto other critical areas of the leadframe or electrical component due to the non-selective nature of the organic coating that is deposited. Such impurities are detrimental to subsequent leadframe and IC assembly process.
- U.S. 2004/0099340 (WO 2004/050959) to Zhang et al. attempts to address the surface oxide problem on metal and metal alloy deposits by incorporating trace amounts of phosphorous in the deposits. Zhang et al. allege that incorporating phosphorous into the deposits reduces the formation of surface oxide on the deposits. The phosphorous compounds are included in the metal and metal alloy electroplating baths, and are co-deposited with the metal or metal alloy. The preferred source of phosphorous is the hypophosphites such as NaH2PO4. A disadvantage of such a method is the inclusion of the hypophosphites in the baths. The more components that are added to a bath, the more likely it is to have undesirable interactions in the bath. The hypophosphite may interact with other functional additives, which may compromise the grain size, crystal orientation, ductility, hardness, and conductivity of the deposit.
- Although there are methods and compositions which address the surface oxide problem on metal and metal alloy deposits, there is still a need for improved compositions and methods for inhibiting surface oxide formation on metals and metal alloys.
- Compositions are provided composed of one or more phosphoric acids or salts thereof in amounts to inhibit oxide formation on metals and metal alloys, and water. In addition to inhibiting oxide formation on metals and metal alloys, the compositions provide a stable grain structure for subsequent soldering. The oxide formation is undesirable since it may cause electrical malfunctions of metal components in electrical devices compromising the performance of the devices. Additionally, the compositions do not contaminate the metals and metal alloys they treat.
- In another embodiment, the compositions consist of one or more inorganic phosphoric acids or salts thereof and one or more organic phosphoric acids and salts thereof in sufficient amounts to inhibit oxide formation on metals or metal alloys, and water.
- In a further embodiment, methods include contacting metals or metal alloys with compositions including one or more phosphoric acids or salts thereof to inhibit oxide formation on the metals or metal alloys.
- In an additional embodiment a method includes depositing one or more metals or metal alloys on a substrate; contacting the one or more metals or metal alloys with a composition including one or more phosphoric acids or salts thereof; and reflowing the one or more metals or metal alloys. The method inhibits the formation of oxide on the metals and metal alloys.
- As used throughout this embodiment, the following abbreviations have the following meanings, unless the context clearly indicates otherwise: ° C.=degrees Centigrade; g=gram; L=liter; mL=milliliter; ASD=amperes/dm2; sec.=seconds; μm=microns; min.=minutes; wt %=weight percent; v/v=volume to volume; and DI=deionized. The terms “depositing” and “plating” are used interchangeably throughout this specification.
- Compositions are composed of one or more phosphoric acids or salts thereof, and water. The compositions inhibit corrosion on metals and metal alloys, and provide a stable grain structure on the surface of the metals and metal alloys for subsequent soldering. Such corrosion is in the form of an oxide which forms on the metals and metal alloys. Typically it forms on a surface of the metals and metal alloys and is discernable by a discoloration. In addition the compositions do not contaminate the metals and metal alloys when they are applied to the metals and metal alloys.
- Any suitable phosphoric acid or salt thereof and mixtures thereof which inhibit oxide formation on metals and metal alloys may be used. Such phosphoric acids include inorganic phosphoric acids such as phosphoric acid (H3PO4), also known as orthophosphoric acid, and polyphosphoric acids. Inorganic phosphoric acids may be represented by the formula: Hn+2PnO3n+1, where n is an integer of 1 or greater. When n is an integer of 2 or greater, the formula represents a polyphosphoric acid. When the inorganic phosphoric acid is a polyphosphoric acid, typically, n is an integer such that the polyphosphoric acid has an average molecular weight of 110 to 1,500 atomic weight units.
- Salts of phosphoric acids such as sodium phosphate and potassium phosphate may be used. The salts include the dibasic sodium phosphate, tribasic sodium phosphate, dibasic potassium phosphate and tribasic potassium phosphate. Salts of the polyphosphoric acids also may be used. Mixtures of the inorganic phosphoric acids and their salts also may be included in the compositions. Such acids are commercially available, or may be made according to methods described in the literature.
- The inorganic phosphoric acids and their salts are included in the compositions in amounts to inhibit formation of oxides on metals and metal alloys. For example, the inorganic phosphoric acids and their salts may be included in the compositions in amounts of 0.1 gm/L to 1500 gm/L, or such as from 0.5 gm/L to 1000 gm/L, or such as from 1 gm/L to 500 gm/L, or such as from 10 gm/L to 100 gm/L, or such as 20 gm/L to 50 gm/L.
- In addition to the inorganic phosphoric acids, organic phosphoric acids also may be used. One or more organic phosphoric acids and salts thereof may be included in the compositions. Examples of such phosphoric acids include alkylphosphoric acids such as (C1-C20)alkyl phosphoric acids, hydroxyalkyldiphosphoric acids and salts thereof, hydroxyalkylenephosphoric acids and salts thereof, hexaalkylenediamino-tetra(alkylene-phosphoric) acids and salts thereof, and aminotris(alkylene-phosphoric) acids and salts thereof, and phosphorocarboxylic acids and salts thereof. Such phosphoric acids are commercially available, or may be made according to methods described in the literature.
- Examples of suitable alkylphosphoric acids include n-hexylphosphoric acid, n-tetradecylphosphoric acid, n-octylphosphoric acid, n-decylphosphoric acid, n-dodecylphosphoric acid, n-octadecylphosphoric acid, n-hexadecylphosphoric acid, methane diphosphoric acid, 1,2-ethanediphosphoric acid, and 1,3-proanediphosphoric acid. Examples of suitable hydroxyalkyldiphosphoric acid are hydroxyethanediphosphoric acid, hydroxymethyl diphosphoric acid and hydroxyethyl diphosphoric acid (HEDP). An example of a suitable hydroxyalkylenediamino-tetra(alkylene-phosphoric) acid is hexamethylenediamino-tetra(methylenephosphoric) acid. An example of an aminotris(alkylene-phosphoric) acid is aminotris(methylene-phosphoric) acid. Examples of phosphorocarboxylic acids include phosphoroacetic acid, 2-phosphoropropionic acid, 2-hydroxy-phosphoroacetic acid, 2-hydroxy-2-methyl phosphoroacetic acid, 2-hydroxy-2-butyl phosphoroacetic acid, 3-phosphoro-3-hydroxy butyric acid, 2-phosphoroethane-1,2-dicarboxylic acid, 2-phosphoro-butane-1,2,4-tricarboxylic acid, 2-amino-phosphoroacetic acid, 2-amino-2-methyl phosphoroacetic acid, and phosphoromethylimino diacetic acid.
- Examples of other suitable organic phosphoric acids include methylamino bis-methylene phosphoric acid, phosphoromethyl glycine, bis-phosphoromethyl glycine, 1-aminoethyl-1,1-diphosphoric acid, hexamethylene diamine tetrakis(methylene phosphoric) acid, diethylene triamine tetra(methylene phosphoric) acid, diethylene triamine penta(methylene phosphoric) acid, bis-hexamethylene triamine pentakis(methylene phosphoric) acid and salts thereof.
- Typically, the aminotris(methylene-phosphoric) acids are used as the organic phosphoric acid, for example aminotris(methylene-phosphoric) acid. It is commercially available as DEQUEST® 2000 and DEQUEST® 2006 (available from Brenntag, Germany).
- The organic phosphoric acids and their salts are included in the compositions in amounts of 0.005 gm/L to 1 gm/L, or such as from 0.01 gm/L to 0.5 gm/L, or such as from 0.1 gm/L to 0.25 gm/L.
- Optionally, phosphorous acid (H3PO3) may be included in the formulation. Phosphorous acid may be included in amounts of 0.1 g/L to 1 g/L.
- The compositions are aqueous and are applied to metals and metal alloys to inhibit the formation of oxides on the metals and the metal alloys. The pH of the compositions is from 1 to 6, or such as from 2 to 4. The compositions may be applied on any metal and metal alloy where oxide formation may be inhibited. Examples of such metals include tin, copper, nickel, silver and alloys thereof. Typically the compositions are used to inhibit oxide formation on tin and its alloys. Examples of tin alloys include tin/lead, tin/copper, tin/silver, tin/silver/copper, tin/nickel, tin/bismuth and tin/gold. More typically they are used to inhibit oxide formation on tin and tin/lead. Most typically they are used to inhibit oxide formation on tin.
- The compositions may be applied to the metals and metal alloys at any period after the metals and metal alloys are deposited on a substrate. Typically they are applied right after the metal or metal alloy plating as a post-treatment process. The oxidation inhibiting action of the compositions may last days after the post-treatment and still be effective when the metal or metal alloy is reflowed. Accordingly, the treated metal or metal alloy may be stored or transported and reflowed latter and still inhibit oxidation.
- Tin may form tin oxide (SnO) after reflow. This is noticeable on the deposited tin after the reflow process by a discoloration of the tin surface. The longer the exposure of the reflowed tin to oxygen and the higher the temperature, the more noticeable is the discoloration. Typically the discoloration is observable as a yellow tint on the surface of the tin. In more severe cases of oxidation, the tin may appear brown and even purple after reflow. Oxidation of the tin may result in poor electrical conduction or shorts in electronic devices where the tin is plated such as in printed wiring boards and leadframes. In addition, the presence of oxidation on the tin or tin alloy surface compromises any subsequent soldering process of the tin or tin alloy. Poor soldering may result in separation of the soldered parts resulting in malfunction of the electronic device. The compositions inhibit the undesirable oxidation, provide a stable grain structure on the surface of the tin, and do not contaminate the tin surface.
- The compositions may be applied to the metals and metal alloys by any suitable method in the art. For example, the compositions may be sprayed on the metals and metal alloys or the metals and metal alloys may be immersed in the compositions. Typically, the metals and metal alloys are immersed in the compositions. Generally, the compositions are at temperatures of 18° C. to 60° C., or such as from 20° C. to 50° C., or such as from 25° C. to 40° C.
- The amount of time the metals and metal alloys are exposed to the oxide inhibiting composition may vary. Typically, the metals and metal alloys are in contact with the compositions for at least 5 sec. before any subsequent processing steps. More typically, the metals and metal alloys are in contact with the composition for 5 sec to 60 sec., or such as from 10 sec. to 30 sec. The metals and metal alloys may then be optionally rinsed with water to remove any excess oxide inhibiting composition.
- A reflow process may follow the treatment and rinse step. Any suitable reflow process may be used. Reflow may be by heating by vapor phase reflow, laser reflow, plasma, oven melting, and passing an electrical current through the metals and metal alloys, or by any other method of heating the metals and metal alloys above their liquidus temperature.
- The compositions may be used with any suitable metal deposition process such as electrolytic metal deposition or electroless metal deposition. The compositions may be used to inhibit oxidation of metals and metal alloys used in the manufacture of any article which is made with electrolytically or electrolessly deposited metals. Examples of such articles include printed wiring boards, connectors, passive components, bumps on wafers and leadframes
- In one embodiment, a substrate, such as a printed wiring board, connectors or leadframe, optionally may be cleaned prior to metallization. Any suitable cleaning process may be used which is acceptable in the metallization arts. Typically, the substrate is ultrasonically cleaned in a suitable solution. Such cleaning solutions may include silicate compounds, alkali metal carbonates and other components such as alkali metal hydroxides, glycol ethers and one or more chelating agents.
- Optionally, following the cleaning step, the substrate may be activated with a suitable acid such as a mineral acid. An example of such an acid is sulfuric acid. However, other mineral acids may be used. The acids are used in conventional concentrations well known in the art.
- The substrate may then be plated with a metal such as tin, copper, nickel, silver or an alloy thereof or, for example, tin may be plated on nickel or tin on copper. Any suitable metal or metal alloy plating bath may be used. For example, a typical tin plating bath may include one or more water soluble tin salts such as tin sulfate, tin alkyl sulfonates such as tin sulfonate, tin alkanol sulfonic acid, and tin halides such as tin chloride. The bath also includes electrolytes such as sulfuric acid, alkyl sulfonates, alkanol sulfonates and halide salts to provide an electro-conductive matrix. Surfactants also may be included as well as other conventional additives to provide a desirable tin layer. The amounts of the components are conventional and are well known in the art and may be obtained from the literature. U.S. Pat. No. 5,174,887 and U.S. Pat. No. 5,871,631 disclose suitable tin electroplating baths. U.S. Pat. No. 4,880,507 and U.S. Pat. No. 4,994,155 disclose suitable tin/lead plating baths.
- A suitable copper electrolytic bath may include one or more water soluble copper salts such as copper sulfate pentahydrate, a sulfuric acid matrix to provide electrical conduction in the bath, chloride ions from sodium chloride or hydrogen chloride, levelers, carriers, brighteners and other additives such as surfactants to provide the desired copper metal layers. The amounts of such components are conventional and are well know in the art and the literature. U.S. Pat. No. 6,652,731 discloses a suitable copper metal electrolyte for electrolytic deposition.
- Any suitable nickel bath may be used. A nickel bath may include one or more water soluble nickel salts such as nickel chloride, nickel sulfate hexahydrate, and nickel sulfamate tetrahydrate. One or more acids such as boric acid and ascorbic acid may be included. Additionally, one or more conventional additives may be included to provide a desired nickel layer. The amounts of the components may be conventional and are well known in the art, or may be obtained from the literature. An example of a suitable nickel electroplating solution is disclosed in U.S. Pat. No. 6,858,122.
- The metals may be deposited at any suitable temperature and current density depending on the metal or metal alloy plated. Generally, the bath temperatures range from 15° C. to 40° C., or such as from 25° C. to 30° C. The current density is typically from 1 ASD to 35 ASD, or such as from 5 ASD to 30 ASD, or such as from 10 ASD to 20 ASD. However, any conventional current density used to plate tin, copper, nickel or alloys thereof may be used. Suitable current densities are disclosed in the literature.
- After the metals or metal alloys are deposited on the substrates, they undergo post-metallization treatment with the oxide inhibition compositions as described above. The treated metals or metal alloys may then be reflowed by one of the methods described above. After reflow the metal or metal alloy plated substrate may be further processed as desired.
- Twelve (12) brass connectors were ultrasonically cleaned at 65° C. for 30 sec. in a cleaning solution containing 100 g/L of RONACLEAN™ GP-300LF(SE), which is a silicate containing cleaning composition (obtainable from Rohm and Haas Electronic Materials L.L.C., Marlborough, Mass., USA).
- After cleaning, each brass connector was removed from the cleaning solution and activated with technical grade sulfuric acid. The brass connectors were immersed in a 100 mL/L of the technical grade sulfuric acid at room temperature for 10 sec. Each brass connector was then nickel plated.
- The 12 brass connectors were joined in electrical communication with a rectifier and an insoluble electrode which functioned as an anode. The brass connectors functioned as cathodes. The anode and the 12 brass connectors were placed in an electrolytic nickel plating solution to complete the circuit. The nickel plating solution was an aqueous solution which included 700 mL/L of nickel sulfamate solution (180 g/L) and 8 g/L of nickel chloride concentrate (500 g/L) to provide an electroplating solution containing 115 g/L to 135 g/L of nickel ions.
- The brass connectors were plated with a 1 μm layer of nickel. Electroplating was done at 55° C. at a current density of 10 ASD for 120 sec. The nickel plated brass connectors were then removed from the nickel electrolytic solution, rinsed with water and then plated with tin.
- Each nickel plated brass connector was then placed in a tin electrolyte solution and joined in electrical communication with a rectifier and an insoluble electrode, which functioned as the anode. The nickel plated brass connectors functioned as cathodes. The tin electrolyte included 60 gm/L of tin ions from tin methane sulfonate and 150 mL/L of 70% methane sulfonic acid as the matrix. The temperature of the tin bath was 15° C. during tin deposition.
- The current density during tin deposition was 10 ASD. Tin plating was done for 30 sec. and a tin layer of 2 μm was deposited on the nickel layer of each brass connector. The tin layer appeared smooth and bright.
- A stock solution of an immersion acid oxide inhibitor composition was prepared by mixing 1200 gm of technical grade (85%) phosphoric acid and 100 gm of aminotris(methylene-phosphoric) acid in water to make a one liter aqueous solution. A 20% v/v aqueous immersion acid composition was then made from the stock solution to be used for a tin plating post treatment.
- A control post treatment composition also was prepared. It included 40% sodium hydroxide, 30% sodium carbonate, 20% sodium metasilicate and 10% sodium tripolyphosphate. The solid materials were mixed with sufficient water to make a 10 g/L solution.
- Nine (9) of the tin and nickel plated brass connectors were immersed in the 20% v/v oxide inhibitor composition for 5 sec. at 50° C. They were then removed and rinsed with water, and then hot air dried at 100° C. Each of the 9 tin and nickel plated brass connectors were than reflowed.
- Three (3) of the tin and nickel plated brass connectors were placed in a Sikama Falcon™ 8500 conduction/convection oven to reflow their tin layers. The temperature profile was 125° C. to 180° C. to 240° C. to 260° C. to 240° C. and then cool down to room temperature. Each connector remained in each temperature zone for 30 sec. After reflow, the connectors were examined for oxidation. A visual scale of 0 to 5 was used. If no visible oxidation was observed, the connector was rated 0; and if there was serious discoloration, the connector was given a 5. One of the connectors was free of any discoloration (0). One had a slight yellow tint (1). One had severe discoloration, which was noticeable by a distinct yellowing of the reflowed tin layer (4).
- Three (3) of the tin and nickel plated brass connectors were placed in the Sikama Falcon™ 8500 conduction/convection oven and reflowed using the same temperature profile and dwell times as the first set of connectors except that they were reflowed twice. The 3 connectors were then allowed to cool to room temperature and their tin surfaces were observed for signs of oxidation. One of the connectors was free of any visible tin oxidation (0). One had severe tin oxidation (4), and one showed a slight yellow tint (1).
- The remaining 3 tin and nickel plated brass connectors, which were treated with the immersion acid composition, were placed in the same conduction/convection oven as the first six but were reflowed three times using the temperature profile above and the dwell times. All three were removed from the oven after reflow and allowed to cool to room temperature. One of the connectors was free of any visible signs of surface oxidation (0). One showed discoloration (4), and one showed noticeable, but not severe discoloration (2).
- The 3 remaining connectors were immersed in the control treatment solution described above. Each connector remained in the solution for 5 sec. at a temperature of 50° C. After they were removed from the treatment solution, they were rinsed with water and hot air dried at 100° C. One was reflowed once using the oven and temperature profile with dwell times described above. The second was reflowed twice and the third was reflowed three times using the temperature profile and dwell times described above.
- Each control connector was removed from the oven after the reflow cycle and allowed to cool to room temperature. Visible observation of each connector showed severe discoloration (4).
- Although some of the tin and nickel plated brass connectors treated with the acid immersion composition showed discoloration, there were still 3 which were completely free of any visible signs of tin oxidation. Additionally, 3 of the connectors showed minor discoloration, while only 3 showed severe discoloration. In contrast, all three of the control connectors treated with the control treatment solution showed severe discoloration. Accordingly, the immersion acid composition containing an inorganic phosphoric acid and an organic phosphoric acid showed improvement in preventing tin oxidation over the controls.
- Sixteen (16) brass connectors were ultrasonically cleaned at 65° C. for 30 sec. in a cleaning solution containing 100 g/L of RONACLEAN™ CP-100S, which is a silicate containing cleaning composition (obtainable from Rohm and Haas Electronic Materials L.L.C., Marlborough, Mass. USA).
- After cleaning, each brass connector was removed from the cleaning solution and activated with technical grade sulfuric acid. The brass connectors were then immersed in a 100 mL/L of the technical grade sulfuric acid at room temperature for 10 sec. Each brass connector was then nickel plated.
- The 16 brass connectors were joined in electrical communication with a rectifier and an insoluble electrode which functioned as an anode. The brass connectors functioned as cathodes. The anode and the 16 brass connectors were placed in an electrolytic nickel plating solution to complete the circuit. The nickel plating solution was an aqueous solution which included 700 mL/L of nickel sulfamate solution (180 g/L) and 8 g/L of nickel chloride concentrate (500 g/L) to provide an electroplating solution containing 115 g/L to 135 g/L of nickel ions.
- The brass connectors were plated with a 1 μm layer of nickel. Electroplating was done at 55° C. at a current density of 10 ASD for 120 sec. The nickel plated brass connectors were then removed from the nickel electrolytic solution, rinsed with water and then plated with tin.
- Each nickel plated brass connector was then placed in tin electrolyte baths and joined in electrical communication with a rectifier and an insoluble electrode, which functioned as the anode. The nickel plated brass connectors functioned as cathodes. The tin electrolyte baths included 60 gm/L of tin ions from tin methane sulfonate and 150 mL/L of 70% methane sulfonic acid as the matrix. All sixteen connectors were plated with tin at 15° C.
- Eight (8) of the connectors in the tin baths were tin plated at a current density of 10 ASD, and 8 of the connectors were tin plated at a current density of 15 ASD. Tin plating was done in each bath for 30 sec. to form a bright tin layer of 2 μm on the nickel layer of each brass connector. After tin plating, the tin and nickel plated brass connectors were removed from their respective baths and rinsed with water and then air dried at room temperature.
- A stock solution of an immersion acid oxide inhibitor was prepared by mixing 1200 gm of technical grade (85%) phosphoric acid and 100 gm of aminotris(methylene-phosphoric) acid in water to make a one liter aqueous solution. From the stock solution, dilute solutions of 5% v/v, 10% v/v, 20% v/v and 30% v/v were made to treat the tin and nickel plated brass connectors.
- Each of the diluted immersion oxide inhibiting compositions was used to treat one connector tin plated at 10 ASD and 20° C. and one connector at 15 ASD and 20° C. and another pair at 50° C. Each tin and nickel plated connector was immersed in the compositions for 5 sec. They were then removed and hot air dried at 100° C.
- Each of the treated connectors was then placed in a Sikama Falcon™ 8500 conduction/convection oven for reflow of the tin layers. The temperature profile was 125° C. to 180° C. to 240° C. to 260° C. to 240° C. and then back down to room temperature. The connectors dwelled in each temperature zone for 30 sec. After reflow, the connectors were visibly examined for any tin oxide formation.
- The visible examination of each of the connectors showed no serious discoloration on any of the connectors. Minor discoloration was observed on 4 of the 8 connectors plated with tin at 15 ASD. In contrast, 2 of the connectors plated with tin at 10 ASD showed minor discoloration. Accordingly, the immersion acid oxide inhibiting compositions inhibit the formation of tin oxide on tin plated substrates after reflow.
Claims (9)
1. A composition consisting essentially of one or more phosphoric acids or salts thereof in amounts to inhibit oxide formation on metals and metal alloys.
2. The composition of claim 1 , wherein the one or more phosphoric acids comprise inorganic phosphoric acids, or organic phosphoric acids.
3. The composition of claim 2 , wherein the organic phosphoric acids comprise alkylphosphoric acids, hydroxyalkyldiphosphoric acids, hydroxyalkylenephosphoric acids, hexaalkylenediamino-tetra(alkylene-phosphoric) acids, aminotris(alkylene-phosphoric) acids, or phosphorocarboxylic acids.
4. A composition consisting of one or more inorganic phosphoric acids or salts thereof, one or more organic phosphoric acids or salts thereof, and water.
5. A method comprising contacting a metal or metal alloy with a composition comprising one or more phosphoric acids or salts thereof to inhibit oxidation of the metal or metal alloy.
6. A method comprising:
a) depositing one or more metals or metal alloys on a substrate;
b) contacting the one or more metals or metal alloys with a composition comprising one or more phosphoric acids or salts thereof; and
c) reflowing the one or more metals or metal alloys.
7. The method of claim 6 , wherein the one or more metals or metal alloys are deposited on the substrate electrolytically.
8. The method of claim 6 , wherein the metal is tin, or the metal alloy is a tin alloy.
9. The method of claim 6 , wherein the substrate is a printed wiring board, lead frame or connector.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0507887.8 | 2005-04-20 | ||
GB0507887A GB0507887D0 (en) | 2005-04-20 | 2005-04-20 | Immersion method |
Publications (1)
Publication Number | Publication Date |
---|---|
US20060237097A1 true US20060237097A1 (en) | 2006-10-26 |
Family
ID=34630921
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US11/407,706 Abandoned US20060237097A1 (en) | 2005-04-20 | 2006-04-20 | Immersion method |
US12/655,333 Abandoned US20100101962A1 (en) | 2005-04-20 | 2009-12-29 | Immersion method |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/655,333 Abandoned US20100101962A1 (en) | 2005-04-20 | 2009-12-29 | Immersion method |
Country Status (8)
Country | Link |
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US (2) | US20060237097A1 (en) |
EP (1) | EP1716949B1 (en) |
JP (1) | JP5121160B2 (en) |
KR (1) | KR101295186B1 (en) |
CN (1) | CN1861842B (en) |
DE (1) | DE602006002419D1 (en) |
GB (1) | GB0507887D0 (en) |
TW (1) | TWI336736B (en) |
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WO2010081833A2 (en) | 2009-01-14 | 2010-07-22 | Atotech Deutschland Gmbh | Solution and process for increasing the solderability and corrosion resistance of a metal or metal alloy surface |
US20100196727A1 (en) * | 2007-07-10 | 2010-08-05 | Atotech Deutschland Gmbh | Solution and process for increasing the solderability and corrosion resistance of metal or metal alloy surface |
US8092559B2 (en) | 2004-05-12 | 2012-01-10 | Luca Technologies, Inc. | Generation of hydrogen from hydrocarbon bearing materials |
US20120148733A1 (en) * | 2009-08-24 | 2012-06-14 | Atotech Deutschland Gmbh | Method for electroless plating of tin and tin alloys |
US20140178711A1 (en) * | 2012-12-26 | 2014-06-26 | Tyco Electronics Corporation | Corrosion resistant barrier formed by vapor phase tin reflow |
US20140308540A1 (en) * | 2013-04-12 | 2014-10-16 | Tyco Electronics Corporation | Plated contact and process of manufacturing plated contact |
US20150020830A1 (en) * | 2013-07-22 | 2015-01-22 | Altria Client Services Inc. | Electronic smoking article |
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US8715978B2 (en) | 2004-05-12 | 2014-05-06 | Transworld Technologies Inc. | Generation of hydrogen from hydrocarbon bearing materials |
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US7696132B2 (en) | 2006-04-05 | 2010-04-13 | Luca Technologies, Inc. | Chemical amendments for the stimulation of biogenic gas generation in deposits of carbonaceous material |
US8770282B2 (en) | 2006-04-05 | 2014-07-08 | Transworld Technologies Inc. | Chemical amendments for the stimulation of biogenic gas generation in deposits of carbonaceous material |
US9458375B2 (en) | 2006-04-05 | 2016-10-04 | Transworld Technologies Inc. | Chemical amendments for the stimulation of biogenic gas generation in deposits of carbonaceous material |
US7977282B2 (en) | 2006-04-05 | 2011-07-12 | Luca Technologies, Inc. | Chemical amendments for the stimulation of biogenic gas generation in deposits of carbonaceous material |
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US9458541B2 (en) * | 2009-08-24 | 2016-10-04 | Atotech Deutschland Gmbh | Method for electroless plating of tin and tin alloys |
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US20140308540A1 (en) * | 2013-04-12 | 2014-10-16 | Tyco Electronics Corporation | Plated contact and process of manufacturing plated contact |
US20150020830A1 (en) * | 2013-07-22 | 2015-01-22 | Altria Client Services Inc. | Electronic smoking article |
US10251422B2 (en) * | 2013-07-22 | 2019-04-09 | Altria Client Services Llc | Electronic smoking article |
US9721913B2 (en) * | 2015-04-17 | 2017-08-01 | Chipmos Technologies Inc | Semiconductor package and method of manufacturing thereof |
Also Published As
Publication number | Publication date |
---|---|
TW200704829A (en) | 2007-02-01 |
CN1861842A (en) | 2006-11-15 |
DE602006002419D1 (en) | 2008-10-09 |
KR101295186B1 (en) | 2013-08-12 |
GB0507887D0 (en) | 2005-05-25 |
EP1716949B1 (en) | 2008-08-27 |
KR20060110813A (en) | 2006-10-25 |
JP2006307343A (en) | 2006-11-09 |
JP5121160B2 (en) | 2013-01-16 |
TWI336736B (en) | 2011-02-01 |
CN1861842B (en) | 2011-08-03 |
EP1716949A1 (en) | 2006-11-02 |
US20100101962A1 (en) | 2010-04-29 |
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