US20010003579A1 - Process for the reduction of copper oxide - Google Patents
Process for the reduction of copper oxide Download PDFInfo
- Publication number
- US20010003579A1 US20010003579A1 US09/075,599 US7559998A US2001003579A1 US 20010003579 A1 US20010003579 A1 US 20010003579A1 US 7559998 A US7559998 A US 7559998A US 2001003579 A1 US2001003579 A1 US 2001003579A1
- Authority
- US
- United States
- Prior art keywords
- approximately
- borane
- range
- reducing agent
- oxide
- 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.)
- Abandoned
Links
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 11
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 11
- 230000009467 reduction Effects 0.000 title description 6
- 230000008569 process Effects 0.000 title description 3
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 39
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 27
- YJROYUJAFGZMJA-UHFFFAOYSA-N boron;morpholine Chemical compound [B].C1COCCN1 YJROYUJAFGZMJA-UHFFFAOYSA-N 0.000 claims abstract description 13
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 12
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 11
- NUGDCSKHHGSKMA-UHFFFAOYSA-N B.c1c[nH]cn1 Chemical compound B.c1c[nH]cn1 NUGDCSKHHGSKMA-UHFFFAOYSA-N 0.000 claims abstract description 5
- JYHRLWMNMMXIHF-UHFFFAOYSA-N (tert-butylamino)boron Chemical compound [B]NC(C)(C)C JYHRLWMNMMXIHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- DTVWWIWHLAXIHG-UHFFFAOYSA-N B.C1CNCCN1 Chemical compound B.C1CNCCN1 DTVWWIWHLAXIHG-UHFFFAOYSA-N 0.000 claims abstract description 4
- DBVMZLIBWOUNHJ-UHFFFAOYSA-N B.COCCN Chemical compound B.COCCN DBVMZLIBWOUNHJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- QELVBRYVPXJQMT-UHFFFAOYSA-N boron;ethane-1,2-diamine Chemical compound [B].NCCN QELVBRYVPXJQMT-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZXEMRGUTUHLXAP-UHFFFAOYSA-N ethylenediaminebisborane Chemical compound [B-][NH2+]CC[NH2+][B-] ZXEMRGUTUHLXAP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 abstract description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229910000085 borane Inorganic materials 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000010019 resist printing Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/63—Treatment of copper or alloys based thereon
-
- 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
- C23C22/83—Chemical after-treatment
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- 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
- H05K2203/03—Metal processing
- H05K2203/0315—Oxidising metal
-
- 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
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1157—Using means for chemical reduction
Definitions
- the present invention relates to a method for the reduction of copper oxide, and, particularly, to a method for reducing copper oxide to improve acid resistance.
- DMAB dimethylamine borane
- the present invention provides a method of treating copper oxide comprising the step of reacting the cupric oxide with a reducing agent selected from the group consisting of morpholine borane (C 4 H 12 BNO), ethylene diamine borane (H 2 NCH 2 CH 2 NH 2 .BH 3 ), ethylene diamine bisborane (H 2 NCH 2 CH 2 NH 2 .2BH 3 ), t-butylamine borane ((CH 3 ) 3 CNH 2 .BH 3 ), piperazine borane (C 4 H 10 N 2 .BH 3 ), imidazole borane (C 3 H 4 N 2 .BH 3 ) and methoxyethylamine borane (C 3 H 9 NO.BH 3 ).
- the reducing agent is morpholine borane.
- the reducing agents of the present invention have been discovered to provide a number of significant advantages over the various reducing agents currently used in the reduction of cupric oxide to cuprous oxide, and particularly over DMAB.
- the thermal stabilities of the reducing agents of the present invention are much better than current reducing agents.
- the reducing agents of the present invention can also react at a very broad temperature range without thermal decomposition.
- the reaction temperature is in the range of approximately 3° C. to approximately 95° C. Reaction at elevated temperatures using the reducing agents of the present invention may decrease the process time over current procedures.
- reducing agents of the present invention are relatively odor free, making handling thereof less noxious.
- the pH value of the aqueous solutions of the reducing agents of the present invention can range from approximately 4 to approximately 14. Preferably, the pH ranges from approximately 7 to approximately 13.
- the concentration range of the reducing agent in the reaction solution is preferably in the range of 0.1 wt % to the solubility limit of the reducing agent in the solvent. More preferably, the concentration range of the reducing agent in the reaction solution is in the range of 0.3 wt % to the solubility limit of the reducing agent in the solvent.
- wt % is defined as follows: weight ⁇ ⁇ of ⁇ ⁇ reducing ⁇ ⁇ agent ( weight ⁇ ⁇ of ⁇ ⁇ reducing ⁇ ⁇ agent + weight ⁇ ⁇ of ⁇ ⁇ solvent ) ⁇ 100 ⁇ ⁇ %
- Copper oxide (cupric oxide) was formed on copper test coupons via well known methods described in the literature or through the use of commercial pre-formulated solutions.
- the weight gain of the oxide coating was typically in the range of approximately 0.30 to 0.50 mg/cm 2 .
- the process cycle included an alkaline soak, water rinse, neutralization, water rinse, sodium hydroxide treatment, and copper oxide treatment.
- the copper oxide immersion time ranged from 4 to 6 minutes at approximately 160 to 170° F.
- Aqueous solutions of the reducing agents of the present invention and deionized water were prepared in a concentration ranging from approximately 1 g/L (1 gram/liter of solution or 0.1 wt %) and higher.
- the concentration of reducing agent was in the range of approximately 0.1 wt % to the solubility limit of the reducing agent.
- the concentration of the reducing agent is more preferably in the range of approximately 1 to approximately 20 gm/L (that is, approximately 0.1 wt % to approximately 2.0 wt %).
- the pH of the solution is in the range of approximately 5 to approximately 13. More preferably, the pH of the solution is in the range of approximately 7 to approximately 13.
- the pH of the solution was adjusted with sodium hydroxide.
- the reaction temperature is preferably in the range of approximately 3° C. to approximately 95° C. More preferably, the reaction temperature is in the range of approximately 20° C. to approximately 50° C.
- a number of protic solvents other than water including alcohols (for example, methanol) are suitable for the reactions of the present invention.
- cupric oxide coated test coupons were immersed in a reducing agent solution as described above. Vigorous bubbling occurred rapidly upon contact with the reducing agent solution. The test coupons were typically immersed for approximately 3 to 10 minutes. The coupon surface was observed to change color from the “black” oxide coating to a uniform brown appearance, indicating the reduction of cupric oxide to cuprous oxide. Subsequent to the reducing reaction, the coupons were rinsed and immersed in 3 molar HCL. The color of the coupon remained the same, indicating it was completely resistant to the aqueous acid solution.
- Table 1 A summary of the results of several experiments performed with morpholine borane over a range of conditions are set forth in Table 1 below.
Abstract
The present invention provides a method of reducing copper oxide to improve its acid resistance comprising the step of reacting cupric oxide with a reducing agent selected from the group consisting of morpholine borane, ethylene diamine borane, ethylene diamine bisborane, t-butylamine borane, piperazine borane, imidazole borane, and methoxyethylamine borane to form cuprous oxide.
Description
- The present invention relates to a method for the reduction of copper oxide, and, particularly, to a method for reducing copper oxide to improve acid resistance.
- A variety of methods have been investigated concerning the surface treatment of copper before bonding a resin to the copper. Under some methods, the surface of a copper printed circuit was chemically treated or polished to form a suitable extent of microscopic irregularities as a pretreatment prior to solder resist printing to improve the bonding strength between the solder resist and the copper circuit. In such treatments, however, there was a problem of copper migration generating electrolytic corrosion deposits, often in the form of dendrites, which results in reduction of the intracircuit spacing. This problem, in turn, led to reduced intracircuit insulation resistance.
- Because sufficient bonding strength between a metal and a resin generally cannot be secured by directly bonding the resin onto the smooth and even surface of the metal, an oxide layer is often formed on the surface of the metal to improve the bonding strength. Accordingly, investigations have been made on a copper surface treatment method in which an oxide layer of cupric oxide (CuO), cuprous oxide (Cu2O), or the like is formed on the surface of copper to improve its bonding strength. Unfortunately, some metallic oxides are readily hydrolyzed upon contact with an aqueous acidic solution and become dissolved therein as metallic ions.
- A number of studies have shown, however, that acid resistance is improved by first forming cupric oxide on the surface of the copper and subsequently reducing the cupric oxide to cuprous oxide. In general, cuprous oxide is less soluble in an acid than cupric oxide. A number of methods of reducing cupric oxide to cuprous oxide have been developed. In U.S. Pat. No. 4,642,161, for example, a solution containing at least one reducing agent represented by the general formula BH3NHRR′, wherein R and R″ are each selected from the group consisting of H, CH3 and CH2CH3, is used to reduce cupric oxide. The most commonly practiced method of reducing cupric oxide to form cuprous oxide, however, is by use of the reducing agent dimethylamine borane (DMAB), which has the formula (CH3)2NH.BH3. See Japanese Patent Application No. 1 219,483 (1989).
- Unfortunately, current methods for the reduction of cupric oxide to form cuprous oxide suffer from a number of significant drawbacks. In general, DMAB and other reducing agents for such a reaction exhibit poor thermal stability and decompose rapidly whenever their temperature reaches a level of approximately 40° C. to 50° C. Moreover, these compounds are often very noxious. Further, the pH for reduction reactions with such compounds typically must be maintained in the limited range of 12 to 13 to prevent hydrolysis of the reducing agent.
- It is, therefore, very desirable to develop a method of reducing cupric oxide to form cuprous oxide which reduces or eliminates these and other drawbacks associated with current methods.
- In general, the present invention provides a method of treating copper oxide comprising the step of reacting the cupric oxide with a reducing agent selected from the group consisting of morpholine borane (C4H12BNO), ethylene diamine borane (H2NCH2CH2NH2.BH3), ethylene diamine bisborane (H2NCH2CH2NH2.2BH3), t-butylamine borane ((CH3)3CNH2.BH3), piperazine borane (C4H10N2.BH3), imidazole borane (C3H4N2.BH3) and methoxyethylamine borane (C3H9NO.BH3). Most preferably, the reducing agent is morpholine borane.
- The reducing agents of the present invention have been discovered to provide a number of significant advantages over the various reducing agents currently used in the reduction of cupric oxide to cuprous oxide, and particularly over DMAB. For example, the thermal stabilities of the reducing agents of the present invention are much better than current reducing agents. The reducing agents of the present invention can also react at a very broad temperature range without thermal decomposition. Preferably, the reaction temperature is in the range of approximately 3° C. to approximately 95° C. Reaction at elevated temperatures using the reducing agents of the present invention may decrease the process time over current procedures.
- Moreover, reducing agents of the present invention are relatively odor free, making handling thereof less noxious. Likewise, the pH value of the aqueous solutions of the reducing agents of the present invention can range from approximately 4 to approximately 14. Preferably, the pH ranges from approximately 7 to approximately 13. The concentration range of the reducing agent in the reaction solution is preferably in the range of 0.1 wt % to the solubility limit of the reducing agent in the solvent. More preferably, the concentration range of the reducing agent in the reaction solution is in the range of 0.3 wt % to the solubility limit of the reducing agent in the solvent. As used herein, wt % is defined as follows:
- Copper oxide (cupric oxide) was formed on copper test coupons via well known methods described in the literature or through the use of commercial pre-formulated solutions. The weight gain of the oxide coating was typically in the range of approximately 0.30 to 0.50 mg/cm2. The process cycle included an alkaline soak, water rinse, neutralization, water rinse, sodium hydroxide treatment, and copper oxide treatment. The copper oxide immersion time ranged from 4 to 6 minutes at approximately 160 to 170° F.
- Aqueous solutions of the reducing agents of the present invention and deionized water were prepared in a concentration ranging from approximately 1 g/L (1 gram/liter of solution or 0.1 wt %) and higher. Preferably, the concentration of reducing agent was in the range of approximately 0.1 wt % to the solubility limit of the reducing agent. In the case of morpholine borane, the concentration of the reducing agent is more preferably in the range of approximately 1 to approximately 20 gm/L (that is, approximately 0.1 wt % to approximately 2.0 wt %).
- Preferably, the pH of the solution is in the range of approximately 5 to approximately 13. More preferably, the pH of the solution is in the range of approximately 7 to approximately 13. The pH of the solution was adjusted with sodium hydroxide. The reaction temperature is preferably in the range of approximately 3° C. to approximately 95° C. More preferably, the reaction temperature is in the range of approximately 20° C. to approximately 50° C. A number of protic solvents other than water including alcohols (for example, methanol) are suitable for the reactions of the present invention.
- During the reduction reaction, cupric oxide coated test coupons were immersed in a reducing agent solution as described above. Vigorous bubbling occurred rapidly upon contact with the reducing agent solution. The test coupons were typically immersed for approximately 3 to 10 minutes. The coupon surface was observed to change color from the “black” oxide coating to a uniform brown appearance, indicating the reduction of cupric oxide to cuprous oxide. Subsequent to the reducing reaction, the coupons were rinsed and immersed in 3 molar HCL. The color of the coupon remained the same, indicating it was completely resistant to the aqueous acid solution. A summary of the results of several experiments performed with morpholine borane over a range of conditions are set forth in Table 1 below.
TABLE 1 Concentration of Acid Morpholine Borane Temperature Resistant (gm/L H2O) (° C.) pH Coating 80 25 7 yes 80 25 13 yes 80 32 7 yes 80 32 13 yes 10 25 7 yes 10 25 13 yes 10 32 7 yes 10 32 13 yes 10 25 4 yes 10 50 4 yes 10 50 14 yes 10 4 7 yes 10 50 7 yes 10 90 7 yes 10 24 4 yes 10 25 14 yes 3 25 7 yes - Table 2 below summarizes several studies performed on compounds other than morpholine borane.
TABLE 2 Conc. Temp. Acid Compound (wt %) (° C.) pH Resistance Appearance piperazine 1.0 23 7-8 Yes Medium borane brown oxide ethylenediamine 1.0 24 7-8 Yes Medium diamine borane brown oxide ethylenediamine 0.75 24 7-8 Yes Dark brown bisborane oxide imidazole borane 1.0 24 7-8 Yes Dark brown oxide methoxyethylamine 1.0 23 7-8 Yes Medium borane brown oxide - Although the present invention has been described in detail in connection with the above examples, it is to be understood that such detail is solely for that purpose and that variations can be made by those skilled in the art without departing from the spirit of the invention except as it may be limited by the following claims.
Claims (20)
1. A method of reducing copper oxide comprising the step of reacting the copper oxide with a reducing agent selected from the group consisting of morpholine borane, ethylene diamine borane, ethylene diamine bisborane, t-butylamine borane, piperazine borane, imidazole borane, and methoxyethylamine borane.
2. The method of wherein the reaction occurs in a solution of the reducing agent wherein the concentration of the reducing agent is in the range of approximately 0.1 wt % to the solubility limit of the reducing agent.
claim 1
3. The method of wherein the concentration of the reducing agent is in the range of approximately 0.3 wt % to the solubility limit of the reducing agent.
claim 2
4. The method of wherein the reaction occurs at temperature in the range of approximately 3° C. to approximately 95° C.
claim 1
5. The method of wherein the reaction occurs at temperature in the range of approximately 20° C. to approximately 50° C.
claim 4
6. The method of wherein the solvent comprises water and the pH of the solution is in the range of approximately 4 to approximately 14.
claim 1
7. The method of wherein the pH of the solution is in the range of approximately 5 to approximately 13.
claim 6
8. The method of wherein the pH of the solution is in the range of approximately 7 to approximately 13.
claim 7
9. The method of wherein reducing agent is morpholine borane.
claim 2
10. The method of wherein concentration of the morpholine borane is in the range of approximately 0.1 wt % to 2.0 wt %.
claim 9
11. A method of reducing cupric oxide to cuprous oxide comprising the step of reacting the copper oxide with a reducing agent selected from the group consisting of morpholine borane, ethylene diamine borane, ethylene diamine bisborane, t-butylamine borane, piperazine borane, imidazole borane, and methoxyethylamine borane.
12. The method of wherein the reaction occurs in a solution of the reducing agent wherein the concentration of the reducing agent is in the range of approximately 0.1 wt % to the solubility limit of the reducing agent.
claim 11
13. The method of wherein the concentration of the reducing agent is in the range of approximately 0.3 wt % to the solubility limit of the reducing agent.
claim 12
14. The method of wherein the reaction occurs at temperature in the range of approximately 3° C. to approximately 95° C.
claim 11
15. The method of wherein the reaction occurs at temperature in the range of approximately 20° C. to approximately 50° C.
claim 14
16. The method of wherein the solvent comprises water and the pH of the solution is in the range of approximately 4 to approximately 14.
claim 11
17. The method of wherein the pH of the solution is in the range of approximately 5 to approximately 13.
claim 16
18. The method of wherein the pH of the solution is in the range of approximately 7 to approximately 13.
claim 17
19. The method of wherein reducing agent is morpholine borane.
claim 12
20. The method of wherein concentration of the morpholine borane is in the range of approximately 0.1 wt % to 2.0 wt %.
claim 19
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/075,599 US20010003579A1 (en) | 1996-06-27 | 1998-05-11 | Process for the reduction of copper oxide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08673201 US5750087B1 (en) | 1996-06-27 | 1996-06-27 | Process for the reduction of copper oxide |
US09/075,599 US20010003579A1 (en) | 1996-06-27 | 1998-05-11 | Process for the reduction of copper oxide |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08673201 Continuation US5750087B1 (en) | 1996-06-27 | 1996-06-27 | Process for the reduction of copper oxide |
Publications (1)
Publication Number | Publication Date |
---|---|
US20010003579A1 true US20010003579A1 (en) | 2001-06-14 |
Family
ID=24701694
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08673201 Expired - Lifetime US5750087B1 (en) | 1996-06-27 | 1996-06-27 | Process for the reduction of copper oxide |
US09/075,599 Abandoned US20010003579A1 (en) | 1996-06-27 | 1998-05-11 | Process for the reduction of copper oxide |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08673201 Expired - Lifetime US5750087B1 (en) | 1996-06-27 | 1996-06-27 | Process for the reduction of copper oxide |
Country Status (7)
Country | Link |
---|---|
US (2) | US5750087B1 (en) |
EP (1) | EP0907763B1 (en) |
JP (1) | JP4212649B2 (en) |
KR (1) | KR100357427B1 (en) |
AU (1) | AU3399997A (en) |
DE (1) | DE69706173T2 (en) |
WO (1) | WO1997049841A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102351237A (en) * | 2011-07-05 | 2012-02-15 | 宁波大学 | Method for preparing nanometer copper oxide |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5753309A (en) * | 1995-12-19 | 1998-05-19 | Surface Tek Specialty Products, Inc. | Composition and method for reducing copper oxide to metallic copper |
ATE256085T1 (en) * | 1997-07-10 | 2003-12-15 | Morton Int Inc | METHOD FOR REDUCING COPPER OXIDE TO METALLIC COPPER |
US6141870A (en) | 1997-08-04 | 2000-11-07 | Peter K. Trzyna | Method for making electrical device |
CA2254362C (en) * | 1998-02-20 | 2004-06-01 | John Fakler | Composition and method for reducing copper oxide to metallic copper |
US6794288B1 (en) | 2003-05-05 | 2004-09-21 | Blue29 Corporation | Method for electroless deposition of phosphorus-containing metal films onto copper with palladium-free activation |
JP5946827B2 (en) | 2010-07-06 | 2016-07-06 | イーサイオニック コーポレーション | Method for manufacturing a printed wiring board |
US9763336B2 (en) | 2010-07-06 | 2017-09-12 | Atotech Deutschland Gmbh | Methods of treating metal surfaces and devices formed thereby |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61176192A (en) * | 1985-01-31 | 1986-08-07 | 株式会社日立製作所 | Adhesion between copper and resin |
US5059243A (en) * | 1989-04-28 | 1991-10-22 | International Business Machines Corporation | Tetra aza ligand systems as complexing agents for electroless deposition of copper |
JPH069309B2 (en) * | 1989-09-22 | 1994-02-02 | 株式会社日立製作所 | Printed circuit board, manufacturing method and manufacturing apparatus thereof |
JPH0496293A (en) * | 1990-08-03 | 1992-03-27 | Risho Kogyo Co Ltd | Manufacture of board for multilayer printed circuit |
IT1256851B (en) * | 1992-01-21 | 1995-12-27 | PROCEDURE FOR PROMOTING ADHERENCE BETWEEN DIFFERENT LAYERS IN THE MANUFACTURE OF MULTILAYER PRINTED CIRCUITS. AND COMPOSITIONS FOR THE IMPLEMENTATION OF THIS PROCEDURE. |
-
1996
- 1996-06-27 US US08673201 patent/US5750087B1/en not_active Expired - Lifetime
-
1997
- 1997-06-16 DE DE69706173T patent/DE69706173T2/en not_active Expired - Lifetime
- 1997-06-16 WO PCT/US1997/010530 patent/WO1997049841A1/en active IP Right Grant
- 1997-06-16 EP EP97930086A patent/EP0907763B1/en not_active Expired - Lifetime
- 1997-06-16 JP JP50327798A patent/JP4212649B2/en not_active Expired - Fee Related
- 1997-06-16 KR KR10-1998-0710318A patent/KR100357427B1/en not_active IP Right Cessation
- 1997-06-16 AU AU33999/97A patent/AU3399997A/en not_active Abandoned
-
1998
- 1998-05-11 US US09/075,599 patent/US20010003579A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102351237A (en) * | 2011-07-05 | 2012-02-15 | 宁波大学 | Method for preparing nanometer copper oxide |
Also Published As
Publication number | Publication date |
---|---|
JP4212649B2 (en) | 2009-01-21 |
KR100357427B1 (en) | 2003-01-15 |
WO1997049841A1 (en) | 1997-12-31 |
DE69706173T2 (en) | 2001-11-29 |
DE69706173D1 (en) | 2001-09-20 |
EP0907763A1 (en) | 1999-04-14 |
US5750087A (en) | 1998-05-12 |
AU3399997A (en) | 1998-01-14 |
US5750087B1 (en) | 1999-12-14 |
KR20000016711A (en) | 2000-03-25 |
EP0907763B1 (en) | 2001-08-16 |
JP2000513410A (en) | 2000-10-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9072203B2 (en) | Solderability enhancement by silver immersion printed circuit board manufacture | |
US4919768A (en) | Electroplating process | |
US8414711B2 (en) | Method of surface treatment for aluminum or aluminum alloy | |
CN101319318B (en) | Electroless gold plating bath, electroless gold plating method and electronic parts | |
USRE45297E1 (en) | Method for enhancing the solderability of a surface | |
USRE45881E1 (en) | Method for enhancing the solderability of a surface | |
CN1057350C (en) | Process for the corrosion protectio of copper or copper alloys | |
US20010003579A1 (en) | Process for the reduction of copper oxide | |
JP3337802B2 (en) | Direct plating method by metallization of copper (I) oxide colloid | |
EP0861923B1 (en) | Activating catalytic solution for electroless plating and method for electroless plating | |
EP0156167A2 (en) | Process for the deposition of a metal from an electroless plating composition | |
EP0152601A1 (en) | Aqueous alcaline bath for chemically plating copper or nickel | |
EP1029944B1 (en) | Method for enhancing the solderability of a surface | |
US7267259B2 (en) | Method for enhancing the solderability of a surface | |
EP0750549B1 (en) | Bismuth coating protection for copper | |
DE60044362D1 (en) | Process for producing an electroplating bath and associated copper plating process | |
JPH0569914B2 (en) | ||
KR102641511B1 (en) | Electroless plating solution and method of copper electroplating | |
USRE45842E1 (en) | Method for enhancing the solderability of a surface | |
GB2253415A (en) | Selective process for printed circuit board manufacturing employing noble metal oxide catalyst. | |
JP4162217B2 (en) | Tin whisker inhibitor and method for producing whisker preventive tin plating using the same | |
JPH02104671A (en) | Palladium activator and method for electroless-plating ceramic substrate | |
JP2004332035A (en) | Electroless nickel-gold plating method | |
JPH0320474A (en) | Electroless copper plating solution | |
JPH05167223A (en) | Manufacture of printed wiring board |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: MINE SAFETY APPLIANCES COMPANY, PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CORELLA, JOSEPH A., II;NEIGH, KEVIN M.;REEL/FRAME:009353/0346 Effective date: 19980511 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |