WO2020148308A1 - Procédé de formation d'oxyde de cuivre sur une surface de cuivre - Google Patents

Procédé de formation d'oxyde de cuivre sur une surface de cuivre Download PDF

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Publication number
WO2020148308A1
WO2020148308A1 PCT/EP2020/050859 EP2020050859W WO2020148308A1 WO 2020148308 A1 WO2020148308 A1 WO 2020148308A1 EP 2020050859 W EP2020050859 W EP 2020050859W WO 2020148308 A1 WO2020148308 A1 WO 2020148308A1
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Prior art keywords
salts
range
oxidizing
compound
mmol
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English (en)
Inventor
Neal Wood
Philipp HAARMANN
Thomas HÜLSMANN
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Priority to KR1020217024779A priority Critical patent/KR102885411B1/ko
Priority to EP20700498.7A priority patent/EP3911781A1/fr
Priority to CN202080009002.0A priority patent/CN113316663A/zh
Priority to JP2021540865A priority patent/JP7462654B2/ja
Publication of WO2020148308A1 publication Critical patent/WO2020148308A1/fr
Anticipated expiration legal-status Critical
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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
    • C23C22/60—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
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • 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
    • 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

Definitions

  • the present invention relates to a method of forming copper oxide on a copper surface and a use of specific oxidizing compounds in an alkaline aqueous oxidizing solution to form uniform copper oxide on a copper surface.
  • passivation is often desired. Passivation may be done for reasons of protection for example by means of a layer of copper oxide.
  • the copper oxide is typically later partially of fully removed for further process steps in the production of the electronic article.
  • solubilization of carbon dioxide from ambi ent air typically leads to a decrease in pH, thereby impairing the performance of the solution in terms of cleaning and oxide formation. This is due to the formation of carbonates in the solution.
  • Aqueous alkaline solutions are known.
  • DE 1546162 A1 discloses such a solution for cleaning work pieces of iron, steel, zink, and alloys thereof.
  • DE 2507056 A1 discloses a solution for cleaning iron-containing metal pieces.
  • US 4,720,332 A relates to the chemical stripping of nickel and nickel alloys from metallic and non-metallic substrates utilizing an aqueous alkaline solution.
  • US 6,036,758 A discloses a composition useful for the surface treatment of copper, in particular for micro-roughening of the copper surface so as to improve the adhesion characteristics of the copper surface, comprises an oxidizing agent for copper and an aromatic sulfonic acid or a salt thereof.
  • the solution is strongly acidic and immediately removes any oxides.
  • the object of the present invention was to provide a method of forming uniform copper oxide on a copper surface, the oxide additionally being quickly obtained, sufficiently thick, and not nega tively affected by the presence of carbonate.
  • the present invention furthermore relates to a use of an oxidizing compound selected from the group consisting of
  • sufficiently thick copper oxide typically a layer of copper(ll)oxide
  • a reasonable contacting time such as up to 20 pg/cm 2 within a few minutes
  • a uniform copper oxide is formed on the copper surface.
  • “uniform” denotes a highly homogeneous copper oxide with a substantially constant thickness and a regular/even copper oxide surface. Therefore, the method of the present invention preferably is a method of forming uniform copper oxide on a copper surface.
  • Step a) providing the substrate:
  • a substrate comprising the copper surface is provided.
  • the copper surface is the surface of a copper deposit, preferably of a copper layer.
  • the copper deposit and the copper layer respectively, preferably comprises 95 atom% or more copper, based on the total number of atoms in the copper deposit and the cop per layer, respectively, more preferably 97 atom% or more, even more preferably 99 atom% or more, most preferably is pure metallic copper. This preferably applies likewise to the copper surface.
  • a method of the present invention is preferred, wherein the cop per surface comprises, in tiny amounts, elements other than copper.
  • the substrate comprising the copper surface is or comprises a non-conductive substrate, preferably is or comprises a resin, a glass, a ceramic, a plastic, a wafer, or combinations thereof, even more preferably the substrate is or comprises a resin, most preferably is or comprises an epoxy resin.
  • step a) the substrate does not com prise a surface of iron and of tin, preferably does not comprise at all iron and tin.
  • the substrate is an electronic article, a part, or a pre-product thereof or is a substrate finally resulting in an electronic article, a part, or a product thereof.
  • the copper surface is a patterned cop per surface, most preferably a patterned copper layer.
  • patterned includes structured, i.e. the copper surface has a three dimensional surface.
  • the copper surface is patterned, wherein in other cases the cop per surface is a copper layer; preferred is in many cases a patterned copper surface.
  • Step b) pre-cleaning the copper surface:
  • the method comprises prior to step c):
  • step b) is optional.
  • a method of the present invention is pre ferred, wherein the method includes said pre-cleaning.
  • pre-cleaning means removal of impurities from the copper surface. Impurities are preferably all other substances than metallic copper. Thus, pre cleaning preferably means to bring the copper surface in a condition that the surface solely or predominantly comprises metallic copper, i.e. Cu°, prior to step c) of the method of the present invention.
  • step b) is done by contacting the copper surface with an aqueous pre-cleaning solution comprising an oxidizing compound different from those defined in step c), and wherein the pre-cleaning solution has a pH of £ 4.
  • the oxidizing compound comprises one or more than one peroxide, preferably one or more than one perox- odisulfate.
  • a peroxide preferably the one or more than one peroxodisulfate, is the only non-metallic oxidizing compound.
  • the oxidizing compound has a total concentration in a range from 0.1 mol/L to 1.5 mol/L, based on the total volume of the pre-cleaning solution, preferably in a range from 0.2 mol/L to 1.2 mol/L, more preferably in a range from 0.3 mol/L to 1.0 mol/L, even more preferably in a range from 0.4 mol/L to 0.9 mol/L, most preferably in a range from 0.5 mol/L to 0.7 mol/L.
  • concentrations are preferably applicable to aforementioned preferred peroxides, most preferably to peroxodisulfates.
  • step b) the pre-cleaning solution has a pH of £ 4, preferably a pH in a range from -2.0 to 4.0, more preferably in a range from -1.0 to 3.9, even more preferably in a range from 0 to 3.8.
  • the pre-cleaning solution has a pH of £ 4, preferably a pH in a range from -2.0 to 4.0, more preferably in a range from -1.0 to 3.9, even more preferably in a range from 0 to 3.8.
  • impurities such as undesired copper oxide are removed to obtain a sufficiently cleansed metallic copper surface prior to step c).
  • step b) the pre-cleaning is carried out by spraying, dipping or rinsing.
  • Step c) contacting with an alkaline aqueous oxidizing solution:
  • the oxidizing solution utilized in step c) of the method of the present invention is an alkaline aqueous solution.
  • aqueous denotes that the oxidizing solution comprises water.
  • Preferred is an oxidizing solution utilized in the method of the present invention, wherein more than 50 vol% of the total volume of the oxidizing solution is water, pref erably 70 vol% or more, more preferably 80 vol% or more, even more preferably 90 vol% or more, most preferably 95 vol% or more.
  • the oxidizing solution comprises water with the proviso that water is the only solvent.
  • alkaline means that the oxidizing solution has a pH of more than 7, preferably of 9 or more, even more preferably of 11 or more, most preferably of 12.5 or more.
  • the oxidizing solution comprises hydroxide ions, preferably in a concentration in a range from 0.1 mol/L to 2.0 mol/L, based on the total volume of the oxidizing solution, preferably in a range from 0.2 mol/L to 1.8 mol/L, even more preferably in a range from 0.3 mol/L to 1.6 mol/L, yet even more preferably in a range from 0.4 mol/L to 1.5 mol/L, most preferably in a range from 0.5 mol/L to 1.2 mol/L.
  • concentrations result in a preferably strong alkaline oxidizing solution, e.g. pH 13 or higher.
  • Preferred is an oxidizing solution comprising one or more than one source of hydroxide ions, preferably one source of hydroxide ions.
  • a preferred source of hydroxide ions is an inorganic hydroxide, an organic hydroxide, or mix tures thereof.
  • An inorganic hydroxide is preferably selected from the group consisting of ammo nium hydroxide and alkaline hydroxides, is preferably selected from the group consisting of ammonium hydroxide, sodium hydroxide, and potassium hydroxide.
  • a preferred organic hydrox- ide is an alkyl ammonium hydroxide, preferably tetra alkyl ammonium hydroxide, more prefera bly tetra methyl ammonium hydroxide.
  • step c) of the method of the present invention contacting is preferably carried out by spray ing, dipping or rinsing, such that the copper surface is partly or entirely in contact with the oxi dizing solution.
  • step c) the copper surface has a (substantially) horizontal or (substantially) vertical orientation.
  • step c) the copper surface has a (substantially) horizontal or (substantially) vertical orientation.
  • step c) is preferably carried out by spraying the oxidizing solution on the copper surface.
  • step c) is preferably carried out by immersing the copper sur face into the oxidizing solution.
  • step c) of the method of the present invention the alkaline aqueous oxidizing solution com prises one or more than one, preferably one, oxidizing compound selected from the group con sisting of
  • the formed copper oxide is directly a result of an oxidation caused by said oxidizing com pound in the alkaline aqueous oxidizing solution.
  • the alkaline aqueous oxidizing solution has its oxidizing capacities as a result of the presence of said one or more than one, preferably one, oxidizing compound.
  • the aromatic sulfonic acid compound comprises one or more than one, preferably one, sulfonic acid group.
  • the aromatic sulfonic acid ester compound comprises one or more than one, pref erably one, esterified sulfonic acid group.
  • Each above mentioned aromatic compound comprises at least one aromatic ring.
  • the oxidizing solu- tion preferably does not comprise a hetero-aromatic compound, most preferably no hetero aromatic compound is utilized in the method of the present invention.
  • said aromatic compounds comprise a benzene moiety, most preferably the only one aromatic ring is a ben zene moiety.
  • Preferred salts of said aromatic compounds are alkali metal salts and ammonium salts, prefera bly sodium and potassium salts.
  • said aromatic compounds are substituted with one or more than one substituent, wherein the one or more than one substituent is connected with the at least one aromatic ring and/or with the sulfonic acid group.
  • Preferred substituents are selected from the group consisting of nitro group, sulfonic acid group, alkoxy group, halogen group, and alkyl group. More preferably, substituents are selected from the group consisting of nitro group, sulfonic acid group, alkoxy group, halogen group, and alkyl group, with the proviso that the ar omatic nitro compound, and salts thereof is not substituted with a sulfonic acid group.
  • the aromatic nitro compound and salts thereof is preferably free of a sulfonic acid group, more pref erably is free of sulfur.
  • a preferred alkyl group is a C1 to C6 alkyl group, preferably C1 to C4, more preferably C1 to C3.
  • a preferred halogen group is chloride and bromide.
  • the one or more than one oxidizing compound comprises a -SO2CI group. This is a preferred representa tive of a substituted aromatic compound, preferably of a substituted aromatic sulfonic acid com pound.
  • a preferred alkoxy group is C1 to C3 alkoxy, preferably methoxy.
  • the one or more than one oxidizing compound comprises a -SO2OCH3 group. This is a pre ferred representative of a substituted aromatic compound, preferably of a substituted aromatic sulfonic acid compound.
  • a preferred substituent for the aromatic sulfonic acid compound, salts thereof, the aromatic sul fonic acid ester compound, and salts thereof is a nitro group, most preferably for the aromatic sulfonic acid compound and salts thereof.
  • Preferred is a method of the present invention, wherein in step c)
  • the aromatic sulfonic acid compound and salts thereof comprise one or more than one (preferably one) nitro group, preferably at least one nitro group being directly attached to an aromatic ring, and/or
  • the aromatic sulfonic acid ester compound and salts thereof comprise one or more than one (preferably one) nitro group, preferably at least one nitro group being directly attached to an aromatic ring.
  • step c) the aromatic nitro compound and salts thereof comprises nitro benzene, salts thereof, substituted nitro benzene and/or salts thereof, preferably nitro benzene and salts thereof.
  • the substituted nitro benzene and salts thereof comprise a substituent, preferably as defined above, preferably with the proviso that the substituted nitro benzene and salts thereof is free of a sulfonic acid group, more preferably is free of sulfur.
  • step c) the one or more than one oxi dizing compound selected from the group consisting of
  • the one or more than one oxidizing compound selected from the group consisting of
  • oxidizing solution constitutes a total molar amount of 96 mol% or more of all oxidizing compounds in the oxidizing solution to oxidize the copper surface, preferably 97 mol% or more, more preferably 98 mol% or more, even more preferably 99 mol% or more, most preferably is the only oxidizing compound, except dissolved molecular oxygen, in the oxidizing solution.
  • the dissolved molecular oxygen is oxygen from ambient air, typically in little concen trations. This oxygen usually dissolves unavoidably in the oxidizing solution.
  • the oxidizing solution com prises substituted benzene sulfonic acid and/or salts thereof, and preferably 96 mol% or more of all aromatic compounds in the oxidizing solution is substituted benzene sulfonic acid and salts thereof, more preferably 97 mol% or more, even more preferably 98 mol% or more, most pref erably 99 mol% or more.
  • step c) the oxidizing solution com prises nitrobenzene sulfonic acid and/or salts thereof, and preferably 96 mol% or more of all aromatic compounds in the oxidizing solution is nitrobenzene sulfonic acid and salts thereof, more preferably 97 mol% or more, even more preferably 98 mol% or more, most preferably 99 mol% or more.
  • the nitro group is preferably in ortho, meta, or para position, most preferably in meta position.
  • step c) an oxidizing solution wherein said one or more than one oxidizing com pound has a total concentration in a range from 5 mmol/L to 500 mmol/L, based on the total volume of the oxidizing solution, preferably in a range from 10 mmol/L to 400 mmol/L, more preferably in a range from 15 mmol/L to 300 mmol/L, even more preferably in a range from 20 mmol/L to 200 mmol/L, yet even more preferably in a range from 25 mmol/L to 100 mmol/L, most preferably in a range from 30 mmol/L to 70 mmol/L.
  • the concentration relates to the total concentration of all these compounds. This preferably applies with the proviso that said one or more than one oxidizing compound is the only oxidizing compound, except dissolved molecular oxygen, in the oxidizing solution.
  • an oxidizing solution comprising one or more than one, preferably one, oxidizing compound selected from the group consisting of an aromatic sulfonic acid com pound and salts thereof (preferably a substituted benzene sulfonic acid compound and salts thereof), wherein said one or more than one oxidizing compound preferably has a total concen tration in a range from 5 mmol/L to 500 mmol/L, based on the total volume of the oxidizing solu tion, preferably in a range from 10 mmol/L to 400 mmol/L, more preferably in a range from 15 mmol/L to 300 mmol/L, even more preferably in a range from 20 mmol/L to 200 mmol/L, yet even more preferably in a range from 25 mmol/L to 100 mmol/L, most preferably in a range from 30 mmol/L to 70 mmol/L.
  • said one or more than one oxidizing compound is the only oxidizing compound, except dissolved molecular oxy gen, in the oxidizing solution.
  • Nitrobenzene sulfonic acid and salts thereof are very preferred oxidizing compounds.
  • the nitro group is preferably in ortho, meta, or para position, most prefer ably in meta position.
  • an oxidizing solution comprising as the one or more than one oxidizing compound 3-nitrobenzene sulphonic acid and/or salts thereof, preferably 3-nitrobenzene sul- phonic acid and/or salts thereof is the only oxidizing compound, except dissolved molecular oxygen, in the oxidizing solution, preferably in a total concentration in a range from 5 mmol/L to 500 mmol/L, based on the total volume of the oxidizing solution, preferably in a range from 10 mmol/L to 400 mmol/L, more preferably in a range from 15 mmol/L to 300 mmol/L, even more preferably in a range from 20 mmol/L to 200 mmol/L, yet even more preferably in a range from 25 mmol/L to 100 mmol/L, most preferably in a range from 30 mmol/L to 70 mmol/L.
  • the oxidizing solution additionally comprises one or more than one complexing agent.
  • the complexing agent typically serves to complex copper ions that are solubilized when applying the oxidizing solution on the copper surface, which avoids formation of insoluble copper hydroxides.
  • a com plexing agent for copper ions prevents or at least significantly reduces such hydroxide for mation.
  • the oxidizing solution additionally comprises one or more than one complexing agent for complexing copper ions, preferably one or more than one complexing agent comprising at least one carboxylic group and at least one hydroxyl group. More preferred is a method of the present invention, wherein in the oxidizing solution the one or more than one complexing agent comprises a sugar, preferably a monomeric sugar.
  • the one or more than one complexing agent for complexing copper ions comprises gluconic acid and/or salts thereof, most preferably the only complexing agent for complexing copper ions in the oxidizing solution is gluconic acid and/or salts thereof.
  • the one or more than one complexing agent has a total concentration in a range from 5 mmol/L to 400 mmol/L, based on the total volume of the oxidizing solution, preferably in a range from 10 mmol/L to 300 mmol/L, more preferably in a range from 15 mmol/L to 200 mmol/L, even more preferably in a range from 20 mmol/L to 100 mmol/L, yet even more preferably in a range from 25 mmol/L to 80 mmol/L, most preferably in a range from 30 mmol/L to 60 mmol/L.
  • the aforementioned concen trations are preferably applicable to aforementioned preferred complexing agents, most prefer ably to gluconic acid and salts thereof.
  • oxidizing solution is substantially free of or does not comprise benzimidazole, preferably is substantially free of or does not com prise an azole.
  • the oxidizing solution is substantially free of or does not comprise hydrogen peroxide, more preferably is substantially free of or does not comprise a peroxide.
  • the oxidizing solution is substantially free of or does not comprise hydrogen peroxide, more preferably is substantially free of or does not comprise a peroxide.
  • oxidizing solution is substantially free of or does not comprise chlorite ions, preferably is substantially free of or does not com prise chlorite ions and hypochlorite ions, most preferably is substantially free of or does not comprise chlorine-oxygen anions.
  • oxidizing solution is substantially free of or does not comprise hypophosphite ions.
  • step c) the time period for the con tacting with the oxidizing solution is in a range from 3 seconds to £ 5 minutes, preferably in a range from 4 seconds to £ 4 minutes, more preferably in a range from 5 seconds to £ 3 minutes, even more preferably in a range from 6 seconds to £ 2 minutes, most preferably in a range from 7 seconds to £ 1 minute.
  • step c) the temperature of the oxidiz ing solution is in a range from 20°C to 80°C, preferably in a range from 25°C to 75°C, more preferably in a range from 30°C to 70°C, even more preferably in a range from 35°C to 65°C, most preferably in a range from 40°C to 60°C.
  • step c) copper oxide is formed on the copper surface in an amount in a range from 10 - 50 pg/cm 2 , preferably in a range from 11 - 45 pg/cm 2 , more preferably in a range from 12 - 40 pg/cm 2 , even more preferably in a range from 13 - 35 pg/cm 2 , most preferably in a range from 14 - 32 pg/cm 2 .
  • step c) the copper oxide forms a uniform copper oxide layer, preferably with a layer thickness in the range from 4 nm to 100 nm, based on copper-(ll)-oxide, preferably in a range from 5 nm to 80 nm, more preferably in a range from 6 nm to 60 nm.
  • a method of the present invention is preferred, wherein after step c) the copper oxide (i) is re moved in an additional step or (ii) is maintained and not removed in an additional step.
  • a method of the present invention comprising further after step c): d) removing the copper oxide, preferably by contacting the copper oxide with an acidic solution.
  • step d typically a very thoroughly cleansed copper surface is obtained.
  • the present invention also relates to a use of an oxidizing compound selected from the group consisting of
  • the present invention preferably also relates to a product obtained or obtainable by the method of the present invention.
  • the product preferably has the properties indicated above.
  • the afore mentioned regarding the method of the present invention preferably applies likewise to the product of the present invention.
  • the product of the present invention is an electronic article, preferably a printed cir cuit board or a wafer.
  • Alkaline aqueous oxidizing solution of the present invention Alkaline aqueous oxidizing solution of the present invention:
  • An oxidizing solution of the present invention (hereinafter simply named“inv”) is produced by adding 10 mmol/L to 50 mmol/L 3-nitrobenzene sulphonate as oxidizing compound to an alka line aqueous solution comprising between 0.5 mol/L and 1 mol/L NaOH (pH 13 to 14) and glu conate as complexing agent.
  • a non-alkaline oxidizing solution comprising between 0.4 mol/L and 0.6 mol/L H2O2 in an aque ous solution having a pH in a range from 4.0 to 4.5 is also prepared for comparative reasons
  • step a) of the method of the present invention copper clad laminates (CCL, EM- 825(l), Elite Material Co., Ltd.; 35 pm copper foil on a non-conductive resin, 7.5 cm x 15 cm) comprising a copper surface, are provided as substrates for the respective experiments.
  • step b) of the method of the present invention the copper surface is pre-cleaned in an aqueous pre-cleaning solution (35°C) comprising sodium peroxydisulfate (SPS), sulfuric ac id, and copper sulfate followed by a rinsing step with water.
  • a pre-cleansed copper surface is obtained exhibiting a pure metallic copper surface.
  • step c) of the method of the present invention the pre-cleansed copper surface is contacted with the respective oxidizing solution at 50°C for 3 minutes contacting time (“inv” and “compl”) or at 35°C for 1 minute contacting time (“comp2”). Characteristics (i) to (iv) are deter mined afterwards. A summary of the results is provided in Table A below.
  • the oxidizing solutions“inv” and “compl” are artificially carbonized by directly introducing gaseous CO2 to finally obtain pre determined carbonate concentrations (volumetric flow-rate approximately 0.5 L/min). For that an almost complete carbonization of the contained hydroxides is carried out. Afterwards, the de sired concentration of carbonate is pH-metrical titrated and carefully checked before each ex periment is carried out. In this way the naturally occurring carbonization facilitated by carbon dioxide from ambient air is simulated. The oxide weight gain (incorporation of oxide) is deter mined depending on the concentration of carbonate. Results are obtained for 3 minutes and 5 minutes contacting time, respectively, in step c).
  • each substrate is rinsed with water and dried at approximately 65°C.
  • n.d. denotes not determined
  • a copper surface contacted with“inv” results in a copper oxide with a significant golden color with a greenish tint (see Table A).
  • This color is characteristic for the method of the present in vention and is basically still formed in an even aged oxidizing solution unless comparatively high carbonate concentrations are reached (see Table B,“inv”, 3 minutes contacting time, 30 g/L carbonate concentration). With 3 minutes contacting time, the characteristic color is maintained for a carbonate concentration from 0 g/L to at least 15 g/L. In contrast, if the contacting time is 5 minutes, the characteristic color is even maintained including a carbonate concentration of 30 g/L (see Table B,“inv”, 5 minutes contacting time).
  • a copper surface contacted with“comp1” results in a copper oxide with an undefined copper color including a dull and/or hazy appearance.
  • This color difference allows a simple optical inspection of copper surfaces treated according to the method of the present invention and easily indicates that the desired copper oxide is pre sent.
  • a substrate contacted with“comp2” shows a strong orange color, which is not further divulg gated in the presence of carbonate.
  • oxidation with H2O2 is comparatively quick (4 sec onds) several disadvantages are clearly observed in our experiments: - copper oxide unacceptably dissolves in the weakly acid oxidizing solution; although the pH is only weakly acidic, undesired dissolution cannot be fully excluded in this step
  • Table A shows that the formation of copper oxide upon contacting with“inv” is initiated signifi cantly earlier compared to contacting with“compl”. Thus,“inv” significantly accelerates the initi ation of copper oxide formation and significantly lowers the initiation time compared to“compl”.
  • Table A shows that contacting with“inv” results in an increased amount of formed copper oxide, which is approximately tripled compared to contacting with“compl” (compare Table A,“compl”, 6 pg/cm 2 vs.“inv”, 18 pg/cm 2 ). Furthermore, Table B shows that in each case more copper ox ide is formed upon contacting with“inv” compared to contacting with“compl”.
  • Homogeneity was determined by visual inspection. A uniformly distributed color (without dark er/brighter areas, spots, blurs and stains) indicates a uniform copper oxide layer. In contrast, a surface with darker/brighter areas of a color including spots, blurs and stains strongly indicates an oxide layer with significantly varying thickness and an obvious inhomogeneity.
  • Table B shows that, in each case, a contacting with“inv” results in a formation of copper oxide. Furthermore, in each case the amount of formed copper oxide is higher compared to a contact ing with“compl”. As a result, formation of copper oxide is not negatively affected by the pres ence of carbonate and increased copper oxide formation also occurs in aged oxidizing solu tions.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Treatment Of Metals (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

La présente invention concerne un procédé de formation d'oxyde de cuivre sur une surface de cuivre, le procédé comprenant les étapes consistant a) à fournir un substrat consistant en la surface de cuivre, b) à nettoyer éventuellement la surface de cuivre, c) à mettre en contact la surface de cuivre avec une solution oxydante aqueuse alcaline consistant en un ou plusieurs composés oxydants choisis dans le groupe constitué d'un composé d'acide sulfonique aromatique, de sels de celui-ci, d'un composé ester d'acide sulfonique aromatique, des sels de celui-ci, d'un composé nitro aromatique et des sels de celui-ci, de sorte que ledit oxyde de cuivre est formé sur la surface de cuivre.
PCT/EP2020/050859 2019-01-15 2020-01-15 Procédé de formation d'oxyde de cuivre sur une surface de cuivre Ceased WO2020148308A1 (fr)

Priority Applications (4)

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KR1020217024779A KR102885411B1 (ko) 2019-01-15 2020-01-15 구리 표면 상에 구리 산화물을 형성하는 방법
EP20700498.7A EP3911781A1 (fr) 2019-01-15 2020-01-15 Procédé de formation d'oxyde de cuivre sur une surface de cuivre
CN202080009002.0A CN113316663A (zh) 2019-01-15 2020-01-15 在铜表面形成氧化铜的方法
JP2021540865A JP7462654B2 (ja) 2019-01-15 2020-01-15 銅表面に酸化銅を形成する方法

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EP19151935.4 2019-01-15
EP19151935 2019-01-15

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WO2020148308A1 true WO2020148308A1 (fr) 2020-07-23

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JP (1) JP7462654B2 (fr)
KR (1) KR102885411B1 (fr)
CN (1) CN113316663A (fr)
TW (1) TWI846799B (fr)
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EP4057782A1 (fr) * 2021-03-12 2022-09-14 Atotech Deutschland GmbH & Co. KG Méthode pour augmenter la force d'adhésion entre le cuivre et un matériau organique et réduire la formation de halo et de vide cunéiforme en modifiant la surface de cuivre et/ou en utilisant des composés de silane hétéroaromatiques

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DE1546162A1 (de) 1964-02-27 1970-04-16 Metallgesellschaft Ag Alkalische waessrige Loesungen fuer die gleichzeitige Reinigung,Entfettung und Beseitigung der Schmiermitteltraegerschicht von Werkstuecken aus Eisen,Stahl,Zink oder deren Legierungen
DE2507056A1 (de) 1975-02-19 1976-09-02 Basf Ag Verfahren zur reinigung von eisen enthaltenden metallgegenstaenden
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FR1294742A (fr) * 1960-01-15 1962-06-01 Rothschilds Continuation Ltd S Perfectionnements apportés au traitement superficiel du cuivre métallique
DE1546162A1 (de) 1964-02-27 1970-04-16 Metallgesellschaft Ag Alkalische waessrige Loesungen fuer die gleichzeitige Reinigung,Entfettung und Beseitigung der Schmiermitteltraegerschicht von Werkstuecken aus Eisen,Stahl,Zink oder deren Legierungen
DE2507056A1 (de) 1975-02-19 1976-09-02 Basf Ag Verfahren zur reinigung von eisen enthaltenden metallgegenstaenden
US4720332A (en) 1986-04-21 1988-01-19 Coffey Barry W Nickel strip formulation
US4720332B1 (fr) 1986-04-21 1990-08-28 W Coffey Barry
US5736065A (en) * 1994-02-02 1998-04-07 Hitachi Chemical Company, Ltd. Chemical reducing solution for copper oxide
US6036758A (en) 1998-08-10 2000-03-14 Pmd (U.K.) Limited Surface treatment of copper

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4057782A1 (fr) * 2021-03-12 2022-09-14 Atotech Deutschland GmbH & Co. KG Méthode pour augmenter la force d'adhésion entre le cuivre et un matériau organique et réduire la formation de halo et de vide cunéiforme en modifiant la surface de cuivre et/ou en utilisant des composés de silane hétéroaromatiques
WO2022189644A1 (fr) * 2021-03-12 2022-09-15 Atotech Deutschland GmbH & Co. KG Procédé pour augmenter la force d'adhérence entre le cuivre et un matériau organique et réduire la formation de halo et de vide en coin par modification de la surface du cuivre et/ou par utilisation de composés silanes hétéroaromatiques
JP2024510986A (ja) * 2021-03-12 2024-03-12 アトテック ドイチェランド ゲーエムベーハー ウント コ カーゲー 銅表面を修飾すること、並びに／又はヘテロ芳香族シラン化合物を使用することにより、銅と有機材料との間において接着強度を増大させるための、また、ハロー及び楔形空間形成を低下させるための方法

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TW202037758A (zh) 2020-10-16
KR102885411B1 (ko) 2025-11-12
EP3911781A1 (fr) 2021-11-24
JP7462654B2 (ja) 2024-04-05
TWI846799B (zh) 2024-07-01
KR20210113636A (ko) 2021-09-16
CN113316663A (zh) 2021-08-27
JP2022517368A (ja) 2022-03-08

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