EP0979208A1 - Composition et procede permettant de reduire l'oxyde de cuivre en cuivre metallique - Google Patents

Composition et procede permettant de reduire l'oxyde de cuivre en cuivre metallique

Info

Publication number
EP0979208A1
EP0979208A1 EP98908643A EP98908643A EP0979208A1 EP 0979208 A1 EP0979208 A1 EP 0979208A1 EP 98908643 A EP98908643 A EP 98908643A EP 98908643 A EP98908643 A EP 98908643A EP 0979208 A1 EP0979208 A1 EP 0979208A1
Authority
EP
European Patent Office
Prior art keywords
borane
cyclic
concentration
composition
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98908643A
Other languages
German (de)
English (en)
Other versions
EP0979208A4 (fr
Inventor
John Fakler
Michael Rush
Scott Campbell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Morton International LLC
Original Assignee
Morton International LLC
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 Morton International LLC filed Critical Morton International LLC
Priority claimed from PCT/US1998/003406 external-priority patent/WO1999042402A1/fr
Publication of EP0979208A1 publication Critical patent/EP0979208A1/fr
Publication of EP0979208A4 publication Critical patent/EP0979208A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof

Definitions

  • the present invention relates to a composition and method for reducing copper oxide to metallic copper in the fabrication of multilayer printed circuit boards.
  • the copper oxide layer is reduced to metallic copper by means of a reducing solution containing an amine borane compound as the active reducing agent.
  • the minute unevennesses created on the copper surface from oxidation remain following reduction, so that the metallic copper surface produced as a result of the reduction process will form a sufficiently strong bond with a resin.
  • the metallic copper surface resulting from the reduction process which is the same black- brown color as the oxide layer, has good acid resistance. Therefore by reducing the copper oxide to metallic copper, the acid resistance of the surface or panel is increased, and there is a reduced likelihood of the appearance of "pink ring".
  • amine boranes represented by the general formula: BH 3 NHRR' (wherein R and R' are each a member selected from the group consisting of H, CH 3 , and CH 2 CH 3 ), such as dimethylamine borane (DMAB) and ammonia borane.
  • DMAB dimethylamine borane
  • this invention provides a composition for reducing a copper oxide layer to metallic copper so as to facilitate bonding a resin to the metallic copper.
  • the composition includes an aqueous reducing solution containing a cyclic borane compound.
  • cyclic borane compounds include morpholine borane, piperidine borane, pyridine borane, piperazine borane, 2,6-lutidine borane, N,N- diethylaniline borane, 4-methylmorphoiine borane, and 1 ,4-oxathiane borane.
  • the present invention provides an improvement to a method of bonding copper and a resin together wherein a copper oxide layer is reduced to metallic copper and the metallic copper is bonded to a resin.
  • the improvement includes reducing the copper oxide layer to metallic copper with an aqueous reducing solution containing a cyclic borane compound. It is an object of the present invention to provide an alternative reducing agent to the amine boranes used for reducing a copper oxide layer to metallic copper so as to facilitate bonding a resin to the metallic copper.
  • the present specification describes a composition and method for reducing copper oxide to metallic copper in the fabrication of multilayer printed circuit boards.
  • copper oxide reduction is particularly useful in the manufacturing of multi-layer printed circuit boards because formation of the oxide layer, which turns the pink copper surface a black-brown color, creates minute unevennesses on the copper surface which provide an interlocking effect between the copper surface and resin, thus improving bonding strength of the layers.
  • copper oxides are soluble in acid, the oxide layer is vulnerable to acid attack.
  • the Akahoshi et al. method solved the problem of the acid vulnerability of the oxide layer.
  • the copper oxide layer is reduced to metallic copper by means of a reducing solution containing an amine borane compound as the active reducing agent.
  • the minute unevennesses created on the copper surface from oxidation remain following reduction, so that the metallic copper surface produced as a result of the reduction process will form a sufficiently strong bond with a resin, and the metallic copper surface resulting from the reduction process, which is the same black-brown color as the oxide layer, has good acid resistance.
  • good acid resistance indicates that the copper oxide layer has been successfully reduced to metallic copper (despite no change in color of the surface), and because such a metallic copper surface retains the minute unevennesses created by the earlier oxidation process, good acid resistance also indicates that the metallic copper surface resulting from the reduction process will have an excellent ability to bond with resins such as those described in the Akahoshi et al. patent.
  • resins include epoxy resins, polyimide resins, polyamide resins, polyester resins, phenolic resins, and thermoplastic resins such as polyethylene, polyphenylene sulfide, polyether-imide resins, and fluororesins.
  • BH 3 NHRR' wherein R and R' are each a member selected from the group consisting of H, CH 3 , and CH 2 CH 3 , as represented below:
  • amine boranes include dimethylamine borane and ammonia borane.
  • amine boranes are expensive; furthermore, after completion of the desired reduction of copper oxide surfaces, the amine boranes are consumed in the reduction solution in amounts greatly in excess of the amount stoichiometrically required for such reduction.
  • reduction of copper oxide by amine borane compounds typically results in high operating costs.
  • an aqueous solution containing a cyclic borane in particular, cyclic borane compounds having nitrogen or sulfur as a ring- forming member, such as the cyclic compound morpholine borane, OC 4 H 8 NH:BH 3 , is very effective in reducing copper oxide to metallic copper so as to facilitate bonding of a resin to the metallic copper in the course of fabrication of multilayer printed circuit boards.
  • the compound morpholine borane contains nitrogen as a ring-forming member, as shown below.
  • Morpholine borane is less expensive to manufacture than the amine boranes, such as DMAB, presently used in the reduction of copper oxide to metallic copper.
  • the melting point of morpholine borane is 98 ° (208° F), compared to DMAB, which has a melting point of 36° (97 °F) .
  • purified morpholine borane can be obtained by distillation at ambient pressure.
  • vacuum distillation must be used, resulting in higher manufacturing costs for morpholine borane as compared to DMAB. This relative ease in manufacturing morpholine borane as compared to amine boranes such as DMAB, results in up to a 50% cost savings, thereby significantly decreasing operating costs for the copper oxide reduction process.
  • the effectiveness of morpholine borane as a reducing agent was determined by processing a copper oxide coated copper panel through a reducing solution containing morpholine borane. Because the metallic copper surface produced from reduction is the same brown-black color as the oxide layer, there are several parameters other than appearance which are measured to test the effectiveness of the reducing process. Such parameters include initiation time, acid resistance, and weight loss of the copper oxide coating after reduction.
  • the initiation time is the time required for the reduction of the copper oxide to initiate.
  • hydrogen bubbles rapidly form from the copper oxide and continue until the reaction is complete; preferably, initiation occurs within 4 minutes.
  • the acid resistance is determined by immersing the reduced copper in an acid bath. Metallic copper survives longer in acid than do copper oxides; one suggested measure of acid resistance is whether the metallic copper layer can withstand acid resistance for at least about 30 minutes.
  • the weight loss of the panel also determines the effectiveness of the reduction process. A copper oxide panel loses weight when the copper oxide is reduced. By measuring the weight loss of the copper oxide panel, the completeness of reduction can be determined .
  • a low weight loss indicates that the copper oxide is not fully being reduced; preferably, weight loss is greater than 1 5%.
  • Copper oxide panels were made by growing an oxide layer on a metallic copper panel. Successful reduction by morpholine borane, as measured by the above parameters, ensures that the minute unevennesses created on the copper surface from oxidation remain following reduction. Those minute unevennesses enable the metallic copper surface produced from morpholine borane reduction to form a sufficiently strong bond with a resin.
  • resins include epoxy resins, polyamide resins, phenoloic resins, and thermoplastic resins such as polyethylene, polyphenylene sulfide, polyether-imide resins, and fluororesins.
  • Example 1 Example 1
  • An aqueous reducing solution was prepared using 1 .6 g/L dimethylamine borane and 1 5.2 g/l sodium hydroxide.
  • the solution at room temperature, was used as a control to reduce copper oxide formed on the above mentioned copper panels by immersing the panels in the reducing solution for a 4 minute dwell time. The initiation time was recorded. The percent weight loss of the copper oxide coating and the time that the resultant coating survived a 1 0 % by volume hydrochloric acid bath were recorded.
  • aqueous reducing solution was prepared using 2.7 g/L morpholine borane and 1 5.2 g/l sodium hydroxide. This was the experimental formula used to determine the effectiveness of morpholine borane as a reducing agent, and contains the stoichiometric equivalent composition of -BH 3 to that contained in a 1 .6 g/L DMAB reducing solution.
  • the panels were immersed in the reducing solution for a 4 minute dwell time. The initiation time was recorded. The percent weight loss of the oxide coating and the time that the resultant coating survived a 1 0 % by volume hydrochloric acid bath were recorded.
  • DMAB and morpholine borane were obtained from Aldrich Chemical Company, Milwaukee, Wisconsin.
  • Sodium hydroxide was obtained from Hill Brothers Chemical Company, Orange, California.
  • the present inventor tested the effectiveness of morpholine borane at other concentrations.
  • the amine borane reducing agents With respect to the amine borane reducing agents, it is known that the amine boranes continue to be consumed even after all of the cupric oxide on the panels has been reduced to copper metal, and no additional cupric oxide is introduced into the solution. Consumption of the amine boranes continues after reduction of the copper oxide panels because, it is theorized, the reduced copper oxide from the panels is still present in the reducing solution, and may be reoxidized or may catalyze the hydrolysis of the amine boranes. Therefore, the amine boranes are consumed in greater than the stoichiomet ⁇ c amount necessary to reduce the copper oxide on the panels. The excessive consumption of the reducing agent shortens the usable lifetime of the reducing solution, and ultimately results in higher operating costs for the process.
  • triazole-containing (C 2 H 3 N 3 ) compounds such as tolytriazole and benzotriazole
  • isoxazole-containing (-C 3 HNO) compounds such as 3-amino-5-
  • the selection of a particular stabilizer and stabilizer concentration is based on several factors, including the following: whether the reduction process stabilized by a given concentration of selected stabilizer is initiated within a reasonable time (preferably in less than about 4 minutes), whether the metallic copper layer resulting from the thus stabilized reduction process is resistant to acid attack (one suggested measure of such resistance is whether the metallic copper layer can withstand acid attack for at least about 30 minutes), and finally, whether the given concentration of selected stabilizer actually results in a decreased consumption of the amine borane reducing agent.
  • thiourea about 1 ppm - 1 3 ppm
  • tolytriazole about 0.50 ppm
  • benzotriazole about 1 .0 ppm
  • 3-amino-5-methylisoxazoie about 1 00 ppm
  • mercaptobenzo-thiazole about 1 0 ppm
  • benzimidazole about 1 0 ppm
  • sulfamic acid about 1 0 g/l
  • the present inventor discovered that copper oxide reduction by morpholine borane can be similarly stabilized so as to reduce consumption of morpholine borane.
  • the morpholine borane reduction process stabilized by thiourea, is initiated in a reasonable time and the metallic copper layer resulting from the stabilized reduction process is resistant to acid attack.
  • a reducing solution consisting of 2.7 g/l morpholine borane and 1 5.2 g/l sodium hydroxide at 80 ° F could be stabilized by the addition of thiourea in a concentration in the range of about 2.5 ppm to about 1 5 ppm.
  • reducing agent concentration and temperature have an effect on the effective concentration range of the stabilizer.
  • reducing agent concentration and temperature have an effect on the effective concentration range of the stabilizer.
  • raising the temperature from about 80° F to 1 20°F increases the upper limit of the effective concentration range of thiourea stabilizer from about 1 5 ppm to about 20 ppm.
  • the present inventor created reducing solutions similar to those used in an actual copper oxide reduction process.
  • the reducing solutions were then poisoned with copper oxide, because during an actual copper oxide reduction process, copper oxide remains in the reducing solution after the reduced copper panels are removed.
  • the remaining copper oxide consumes further amounts of the reducing agent, resulting in overall consumption of reducing agent in greater than the stoichiometric amount necessary for reduction of copper oxide on the panels.
  • the consumption of reducing agent per gram of copper oxide and the consumption of reducing agent per time could be determined.
  • the possible negative effects the potential stabilizer could have on the copper oxide reduction process were determined by processing a copper oxide panel through the reducing solution containing a given potential stabilizer. As described above, there were several parameters examined to determine the effectiveness of such stabilized reducing processes; reduction process initiation time, acid resistance of the metallized copper surfaces resulting from the stabilized reduction, and weight loss of the copper oxide coating after reduction. Initiation time is the time required for copper oxide reduction to begin. When the reduction reaction begins, hydrogen bubbles rapidly form and continue until the reaction is complete. Acid resistance was determined by immersing the resulting metallized copper surface in an acid bath. Metallic copper survives longer than copper oxides in an acid bath. Thus, the effectiveness of a given stabilized reduction process in producing the desired metallic copper surface, was determined by resistance to acid attack.
  • Weight loss of the tested panel also determines the effectiveness of the reduction process. Copper oxide loses weight when it is chemically reduced to copper metal. By measuring the weight loss of the panels, the completeness of reduction was determined. A low weight loss indicates that the copper oxide is not fully being reduced. Copper oxide panels were made by growing an oxide layer on a metallic copper panel.
  • Example 3 To test the effect of the potential reducing stabilizer thiourea, an aqueous reducing solution was prepared using 2.7 grams per liter morpholine borane and 1 5.2 g/L sodium hydroxide. DMAB was obtained from Aldrich Chemical Company, Milwaukee, Wisconsin. Sodium hydroxide was obtained from Hill Brothers Chemical Company, Orange, California. That solution, at room temperature, was used as the control solution. An experimental solution was prepared by adding 2.5 ppm of thiourea to
  • Example 4 The effective stabilization range of thiourea for morpholine borane was tested to a solution of 2.7 g/L morpholine borane and 1 5.2 g/L sodium hydroxide, thiourea was added at 5 ppm intervals, and the solution's ability to reduce copper oxide and stability were determined. The measured parameters were initiation time, percent weight loss, acid resistance, and consumption over 24 hours. The results are presented in Table 4.
  • Example 5 In this example, the concentrations of both morpholine borane and thiourea were varied. Reducing solutions of (1) 8.4 g/L MB, 15.2 g/L sodium hydroxide, and (2) 16.8 g/L MB, 1.2 g/L sodium hydroxide were made. Thiourea was added over the side of the reducing baths, and the reduction of copper oxide panels was determined. The measured parameters were initiation time, percent weight loss, and acid resistance. The results are presented in Table 5.
  • thiourea may be used as a stabilizer in a morpholine borane reducing solution at concentrations ranging from greater than 0 ppm thiourea to 1 60 ppm. Based on the trends evident from these results, it is probable that reducing solutions of morpholine borane having concentrations greater than 1 6.8 g/L MB may still use thiourea as a stabilizer at concentrations greater than 1 60 ppm thiourea.
  • Example 6 As seen in Example 5, Table 5, the effective concentration range of stabilizer in the reducing solution is dependent on the concentration of reducing agent. The effective concentration range of stabilizer in the reducing solution is also dependent on the temperature of the reducing solution.
  • Morpholine borane stabilized with thiourea shows more stability after the reducing bath has been continuously processed and replenished than a comparable DMAB reducing solution stabilized with thiourea which has been continuously processed and replenished.
  • DMAB reduction a reducing bath containing 1 .5 g/L DMAB and 1 5.2 g/L NaOH is initially made. Copper oxide panels are then processed through the reducing bath. The copper oxide is reduced
  • the typical concentration of DMAB used for reducing copper oxide panels is 1 .6 g/L DMAB. Therefore, an automatic control system is set up to replenish the DMAB and keep a constant concentration of 1 .6 g/L DMAB. As replenishment continues, the dimethylamine side product accumulates in the tank. Therefore, a constant concentration of DMAB is present in the reducing solution, 1 .6 g/L DMAB, but the concentration of the dimethylamine functional group is continuously increasing.
  • the concentration of the dimethylamine functional group reaches an equilibrium when the amount of the dimethylamine functional group being formed is equivalent to the amount of dimethylamine being dragged out of the reducing solution on the panels. (It is a rough estimate that 1 0 - 1 5 mL of reducing solution per square foot of panel is dragged out of the reducing solution tank.)
  • the process should finally be in equilibrium with respect to the dimethylamine functional group. That is there should be 1 .6 g/L DMAB, 1 5.2 g/L NaOH, and probably a constant concentration of dimethylamine functional group side product, and probably a constant concentration of a boron containing side product resulting from the reduction process. This more accurately represents the reducing bath as it will be run in the process.
  • the bath is initially made up of 1 .6 g/L DMAB and 1 5.2 g/L NaOH. To mimic equilibrium, which is reached in approximately 20 days, copper oxide is added to the initial bath to decrease the concentration of DMAB in half over 24 hours. This is continued until the DMAB is replenished 20 times. The sum total of the 20 replenishments of 1 /2 the initial concentration has been designated "1 0 turnovers," an initial bath is designated "zero
  • the above scenario is similar for morpholine borane, MB.
  • the initial concentration of morpholine borane is 2.7 g/L MB and 1 5.2 g/L NaOH. Side product formed during the reduction of copper oxide is probably the morpholine complex.
  • the morpholine borane As the morpholine borane is replenished during the reduction process, the morpholine borane remains at a constant concentration of 2.7 g/L MB, but the concentration of the suspected side product, the morpholine complex, continues to increase until the bath reaches equilibrium with respect to the morpholine complex. Testing for the same parameters as was done above with respect to DMAB was done initially and after 20 replenishments of morpholine borane.
  • the stabilizer is added back with the DMAB or the morpholine borane, depending on which reducing agent is used. For example, the concentration of thiourea is initially 2.5 ppm, then the actual concentration of thiourea starts at 2.5 ppm and increases with each replenishment of DMAB or morpholine borane, as the case may be, until equilibrium is reached.
  • the present inventor discovered that there are cyclic borane compounds in addition to morphine borane which are very effective in reducing copper oxide to metallic copper so as to facilitate bonding of a resin to the metallic copper in the course of fabrication of multilayer printed circuit boards.
  • the cyclic borane compounds include piperidine borane, pyridine borane, piperazine borane, 2,6-lutidine borane, 4-ethylmorpholine borane, N,N-diethylaniline borane, 4-methylmorpholine borane, and 1 ,4-oxathiane borane.
  • piperidine borane pyridine borane
  • piperazine borane 2,6-lutidine borane
  • 4-ethylmorpholine borane N,N-diethylaniline borane
  • 4-methylmorpholine borane 4-methylmorpholine borane
  • 1 ,4-oxathiane borane 1 ,4-oxathiane bo
  • 1 9 compounds (in other words, all except N,N-diethylaniline borane) contain nitrogen or sulfur as a ring-forming member.
  • the effectiveness of the above cyclic borane compounds as reducing agents was determined by processing a copper oxide coated copper panel through a reducing solution containing the cyclic borane compound. Because the metallic copper surface produced from reduction is the same brown-black color as the oxide layer, there were several parameters other than appearance which were measured to test the effectiveness of the reducing process. Such parameters included initiation time, acid resistance, and weight loss of the copper oxide coating after reduction.
  • the initiation time is the time required for the reduction of the copper oxide to initiate. When the reduction reaction initiates, hydrogen bubbles rapidly form from the copper oxide and continue until the reaction is complete; preferably, initiation
  • the acid resistance was determined by immersing the reduced copper in an acid bath.
  • Metallic copper survives longer in acid than do copper oxides; one suggested measure of acid resistance is whether the metallic copper layer can withstand acid resistance for at least about 30 minutes.
  • the weight loss of the panel also determines the effectiveness of the reduction process.
  • a copper oxide panel loses weight when the copper oxide is reduced. By measuring the weight loss indicates that the copper oxide is not fully being reduced; preferably, weight loss is greater than 1 5% .
  • Copper oxide panels were made by growing an oxide layer on a metallic copper panel.
  • cyclic borane compounds Successful reduction by the cyclic borane compounds, as measured by the above parameters, ensures that the minute unevenness created on the copper surface from oxidation remain following reduction. Those minute unevenness enable the metallic copper surface produced from the cyclic borane compound reduction to form a sufficiently strong bond with a resin.
  • resins include epoxy resins, polyamide resins, phenoloic resins, and thermoplastic resins such as polyethylene, polyphenylene sulfide, polyether-imide resins, and fluorocesins.
  • Example 7 An aqueous reducing solution was prepared using 25 g/L dimethylamine borane. The solution, at room temperature, was used as a control to reduce copper oxide formed on the above-mentioned copper panels by immersing the panels in the reducing solution for a 4-minute dwell time. The initiation time was recorded. The percent weight loss of the copper oxide coating and the time that the resultant coating survived a 10% by volume hydrochloric acid bath were recorded.
  • aqueous reducing solution was prepared using 42 g/L piperidine borane. This was the experimental formula used to determine the effectiveness of piperidine borane as a reducing agent, and contains the stoichiometric equivalent composition of -BH 3 to that contained in the control solution, a 25 g/L DMAB reducing solution. The panels were immersed in the reducing solution for a 4-minute dwell time. The initiation time was recorded. The percent weight loss of the oxide coating and the time that the resultant coating survived a 1 0% by volume hydrochloric acid bath were recorded.
  • An aqueous reducing solution was prepared using 25 g/L dimethylamine borane.
  • the solution at room temperature, was used as a control to reduce copper oxide formed on the above-mentioned copper panels by immersing the panels in the reducing solution for a 4-minute dwell time. The initiation time was recorded. The percent weight loss of the copper oxide coating and the time that the resultant coating survived a 1 0% by volume hydrochloric acid bath were recorded.
  • Aqueous solutions of each experimental borane compound were made, containing the stoichiometric equivalent composition of -BH 3 to that contained in the control, a 25 g/L DMAB reducing solution.
  • the experimental borane compounds included morpholine borane, piperidine borane, pyridine borane, piperazine borane,
  • 2,6-lutidine borane about 1 .2 g/L to saturation
  • 4-ethylmorpholine borane about 1 .3 g/L to saturation
  • N,N-diethylaniline borane about 1 .3 g/L to saturation
  • 4-methylmorphine borane about 1 .1 g/L to saturation
  • Example 10 (Prophetic) The procedures followed in the General Procedures for Testing Stabilizers and in Examples 3-6 will be used, except that the following cyclic boranes will be substituted for morpholine borane in respective testings of each cyclic borane: piperidine borane pyridine borane piperazine borane

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

L'invention concerne une composition qui permet de réduire une couche d'oxyde de cuivre en cuivre métallique, de façon à faciliter l'adhésion d'une résine sur ledit cuivre métallique. La composition est une solution réductrice aqueuse qui contient un composé cyclique du borane, par exemple des composés dans lesquels l'élément formateur de cycle est l'azote ou le soufre, tels que le morpholine borane, le pipéridine borane, le pyridine borane, le pipérazine borane, le 2,6-lutidine borane, le 4-méthylomorpholine borane, le 1,4-oxathiane borane et le N,N-diéthylaniline borane.
EP98908643A 1998-02-20 1998-02-20 Composition et procede permettant de reduire l'oxyde de cuivre en cuivre metallique Withdrawn EP0979208A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1998/003406 WO1999042402A1 (fr) 1996-04-03 1998-02-20 Composition et procede permettant de reduire l'oxyde de cuivre en cuivre metallique

Publications (2)

Publication Number Publication Date
EP0979208A1 true EP0979208A1 (fr) 2000-02-16
EP0979208A4 EP0979208A4 (fr) 2000-10-25

Family

ID=22266436

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98908643A Withdrawn EP0979208A4 (fr) 1998-02-20 1998-02-20 Composition et procede permettant de reduire l'oxyde de cuivre en cuivre metallique

Country Status (4)

Country Link
EP (1) EP0979208A4 (fr)
JP (1) JP3718722B2 (fr)
KR (1) KR100369489B1 (fr)
CA (1) CA2254362C (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109072438B (zh) * 2016-05-04 2021-08-13 德国艾托特克公司 沉积金属或金属合金到衬底表面及包括衬底表面活化的方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB917006A (en) * 1959-02-27 1963-01-30 Callery Chemical Co Reduction of organic compounds
JPS61221394A (ja) * 1985-03-27 1986-10-01 C Uyemura & Co Ltd 電気めつき方法
US4886924A (en) * 1988-10-17 1989-12-12 The Dow Chemical Company Stereospecific synthesis of [E]-alkenes from enamines via hydroboration
EP0552830A1 (fr) * 1992-01-21 1993-07-28 ALFACHIMICI s.r.l. Procédé pour promouvoir l'adhérence entre différentes couches dans la fabrication des circuits imprimés feuilletés, et compositions pour la mise-en-oeuvre de ce procédé
WO1997049841A1 (fr) * 1996-06-27 1997-12-31 Mine Safety Appliances Company Procede de reduction d'oxyde de cuivre
US5753309A (en) * 1995-12-19 1998-05-19 Surface Tek Specialty Products, Inc. Composition and method for reducing copper oxide to metallic copper
WO1999002452A1 (fr) * 1995-12-19 1999-01-21 Morton International, Inc. Composition et procede permettant de reduire l'oxyde de cuivre en cuivre metal
EP0938447A1 (fr) * 1997-07-10 1999-09-01 Morton International, Inc. Composition et procede permettant de reduire l'oxyde de cuivre en cuivre metal

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2718988A1 (de) * 1976-04-28 1977-11-10 Fuji Photo Film Co Ltd Verfahren zur intensivierung photographischer silberbilder durch physikalische entwicklung sowie verbesserte physikalische entwicklerloesung zur anwendung hierbei

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB917006A (en) * 1959-02-27 1963-01-30 Callery Chemical Co Reduction of organic compounds
JPS61221394A (ja) * 1985-03-27 1986-10-01 C Uyemura & Co Ltd 電気めつき方法
US4886924A (en) * 1988-10-17 1989-12-12 The Dow Chemical Company Stereospecific synthesis of [E]-alkenes from enamines via hydroboration
EP0552830A1 (fr) * 1992-01-21 1993-07-28 ALFACHIMICI s.r.l. Procédé pour promouvoir l'adhérence entre différentes couches dans la fabrication des circuits imprimés feuilletés, et compositions pour la mise-en-oeuvre de ce procédé
US5753309A (en) * 1995-12-19 1998-05-19 Surface Tek Specialty Products, Inc. Composition and method for reducing copper oxide to metallic copper
WO1999002452A1 (fr) * 1995-12-19 1999-01-21 Morton International, Inc. Composition et procede permettant de reduire l'oxyde de cuivre en cuivre metal
WO1997049841A1 (fr) * 1996-06-27 1997-12-31 Mine Safety Appliances Company Procede de reduction d'oxyde de cuivre
EP0938447A1 (fr) * 1997-07-10 1999-09-01 Morton International, Inc. Composition et procede permettant de reduire l'oxyde de cuivre en cuivre metal

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 011, no. 063 (C-406), 26 February 1987 (1987-02-26) & JP 61 221394 A (C UYEMURA & CO LTD), 1 October 1986 (1986-10-01) *
See also references of WO9942402A1 *

Also Published As

Publication number Publication date
EP0979208A4 (fr) 2000-10-25
CA2254362C (fr) 2004-06-01
KR100369489B1 (ko) 2003-04-10
JP3718722B2 (ja) 2005-11-24
JP2001527503A (ja) 2001-12-25
KR20000065234A (ko) 2000-11-06
CA2254362A1 (fr) 1999-08-20

Similar Documents

Publication Publication Date Title
US5721014A (en) Composition and method for reducing copper oxide to metallic copper
US9072203B2 (en) Solderability enhancement by silver immersion printed circuit board manufacture
US7645393B2 (en) Metal surface treatment composition
US7563315B2 (en) Composition and method for preparing chemically-resistant roughened copper surfaces for bonding to substrates
JP5307117B2 (ja) 銅の表面処理剤および表面処理方法
US5753309A (en) Composition and method for reducing copper oxide to metallic copper
US5900186A (en) Composition and method for reducing copper oxide to metallic copper
JP4783484B2 (ja) 無電解金メッキ溶液および方法
US20040099637A1 (en) Composition for producing metal surface topography
US5925174A (en) Composition and process for treating the surface of copper-containing metals
EP0979208A1 (fr) Composition et procede permettant de reduire l'oxyde de cuivre en cuivre metallique
US6746547B2 (en) Methods and compositions for oxide production on copper
EP0938447B1 (fr) Procédé de réducion de l0oxyde de cuivre en cuivre métalliquei
EP0582336B1 (fr) Procédé amélioré de dépÔt chimique de cuivre
EP0378407A1 (fr) Solution de cuivre pour le placage sans courant
US6322656B1 (en) Method and composition for amine borane reduction of copper oxide to metallic copper
JPH05148662A (ja) 無電解銅めつき液
US20030178391A1 (en) Composition for producing metal surface topography
GB2134931A (en) Non-electrolytic copper plating for printed circuit board
JPS60194081A (ja) 改良された無電解銅めつき浴及び方法
KR20010009432A (ko) 산을 주재로한 인쇄회로기판용 화성피막조성물
JPH0323634B2 (fr)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990924

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FI FR GB IT LI NL SE

RIN1 Information on inventor provided before grant (corrected)

Inventor name: CAMPBELL, SCOTT

Inventor name: RUSH, MICHAEL

Inventor name: FAKLER, JOHN

A4 Supplementary search report drawn up and despatched

Effective date: 20000913

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH DE ES FI FR GB IT LI NL SE

RIC1 Information provided on ipc code assigned before grant

Free format text: 7C 01B 6/06 A, 7B 05D 5/00 B, 7B 05D 3/00 B, 7C 23C 22/83 B, 7H 05K 3/38 B

17Q First examination report despatched

Effective date: 20010620

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20060906