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EP0309031A1 - Bäden und Verfahren zum chemischen Polieren von Oberflächen aus Kupfer oder Kupferlegierungen - Google Patents

Bäden und Verfahren zum chemischen Polieren von Oberflächen aus Kupfer oder Kupferlegierungen Download PDF

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Publication number
EP0309031A1
EP0309031A1 EP88201981A EP88201981A EP0309031A1 EP 0309031 A1 EP0309031 A1 EP 0309031A1 EP 88201981 A EP88201981 A EP 88201981A EP 88201981 A EP88201981 A EP 88201981A EP 0309031 A1 EP0309031 A1 EP 0309031A1
Authority
EP
European Patent Office
Prior art keywords
baths
aqueous solution
copper
bath
polishing
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Withdrawn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
EP88201981A
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English (en)
French (fr)
Inventor
Daniel Tytgat
Stefaan Magnus
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.)
Solvay SA
Original Assignee
Solvay SA
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 Solvay SA filed Critical Solvay SA
Publication of EP0309031A1 publication Critical patent/EP0309031A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals
    • C23F3/06—Heavy metals with acidic solutions

Definitions

  • the subject of the present invention is the composition of baths for the chemical polishing of copper or copper alloy surfaces.
  • Chemical polishing of metal surfaces is a well-known technique (electrolytic and chemical polishing of metals - W.J. Mc G. TEGART - Dunod - 1960 - p. 122 et seq.); it consists of treating the metal surfaces to be polished with oxidizing baths.
  • aqueous baths of orthophosphoric acid, nitric acid and acetic acid were used (dito: pages 135 and 136). These baths require high working temperatures, of the order of 50 to 80 ° C and intense mechanical stirring. They also attack the metal at high speed, limiting the duration of polishing to less than five minutes.
  • These particularities of these known baths constitute disadvantages: on the one hand, their use is accompanied by toxic gaseous emissions, on the other hand, their high speed of action and the need to subject them to mechanical agitation makes control difficult and random polishing.
  • aqueous baths have been proposed comprising hydrogen peroxide and a mixture of nitric, phosphoric and hydrochloric acids.
  • Baths have also been proposed comprising, in aqueous solution, phosphoric acid, hydrogen peroxide, hydrochloric acid and 2,6-di-tert-butyl-4-N, N-dimethyl-aminomethylphenol (SU-A-1211338 (ORG. PHYS. CHEM. INST.)).
  • phosphoric acid hydrogen peroxide
  • hydrochloric acid 2,6-di-tert-butyl-4-N, N-dimethyl-aminomethylphenol
  • SU-A-1211338 ORG. PHYS. CHEM. INST.
  • the invention aims to remedy the aforementioned drawbacks of known polishing baths, by providing novel bath compositions for the chemical polishing of copper and copper alloys, which have a moderate speed of action, do not require a working temperature. excessive nor intense mechanical agitation and ensure polishes of higher quality than that of polishes obtained with known baths.
  • the invention therefore relates to baths for the chemical polishing of copper or copper alloy surfaces, which comprise, in aqueous solution, hydrogen peroxide, chloride ions and a mixture of phosphoric acid, phosphate ions and hydrogen phosphate ions in respective amounts adjusted to give the aqueous solution a pH value of between 1.25 and 3.
  • the hydrogen peroxide serves as an oxidizing agent for the metal to be polished.
  • chloride ions The function of chloride ions is to protect the metal from anarchic local corrosion during the polishing treatment. They can be used in the form of all water-soluble compounds such as hydrochloric acid or alkali metal chloride. Sodium chloride is preferred.
  • the phosphate and hydrogen phosphate ions are anions of general formula: (H x PO4) (3-x) - where x is between 0 and 2.
  • the baths according to the invention can contain mixtures of these anions. These can be used in the form of any water-soluble inorganic compounds, such as alkali metal salts.
  • the respective amounts of phosphoric acid and of phosphate and hydrogen phosphate anions are chosen so as to give the aqueous solution of the bath, a pH value of between 1.25 and 3, as obtained. by mathematical calculation from the contents of phosphoric acid and of phosphate and hydrogen phosphate anions in the aqueous solution. This imposed pH value differs from the actual value actually measured which depends in particular on the content of hydrogen peroxide and chloride ions in the aqueous solution. Thereafter, unless otherwise stated, the pH values mentioned will be calculated theoretical values as defined above.
  • the respective contents of hydrogen peroxide, chloride ions, phosphoric acid and phosphate and hydrogen phosphate salts are chosen according to the nature of the metal treated, the working temperature and the desired duration for the polishing treatment.
  • Baths which are well suited in the majority of applications are those in which the hydrogen peroxide content is between 1 and 6 moles per liter of the aqueous solution and the chloride ion content is between 10 ⁇ 4 and 1 mole per liter.
  • Preferred baths are those in which the aqueous solution has a pH value of between 1.65 and 2.35 and comprises: - hydrogen peroxide in an amount between 3 and 5 moles / l; - chloride ions in an amount between 5.10 ⁇ 3 and 5.10 ⁇ 2 mole / l; - phosphoric acid and the phosphate and hydrogen phosphate ions in respective molar quantities in accordance with the following relationships:
  • the aqueous solution of the baths according to the invention may contain, in usual proportions, additives commonly present in aqueous baths for the chemical polishing of metals, for example surfactants, viscosity regulators and stabilizers of peroxide. 'hydrogen.
  • additives commonly present in aqueous baths for the chemical polishing of metals for example surfactants, viscosity regulators and stabilizers of peroxide. 'hydrogen.
  • the chemical polishing baths according to the invention make it possible to produce surface polishes of excellent quality, in particular greater than that of the polishes obtained with the polishing baths described in document SU-A-1211338.
  • a great advantage of the polishing baths according to the invention lies in their ability, after adaptation of the respective concentrations of their constituents, to carry out polishing at moderate speed of action, which can be distributed over several hours, so as to allow uniform polishing. large surfaces or hard to reach surfaces.
  • the baths according to the invention are suitable for polishing all surfaces of copper or copper alloys, such as brass and bronze, for example.
  • the invention therefore also relates to a method for polishing the surface of a copper or copper alloy object, according to which the surface to be polished is brought into contact with a polishing bath according to the invention.
  • the polishing bath can be used at all temperatures and pressures for which there is no risk of degrading its constituents. However, it has proved advantageous to use the bath at atmospheric pressure, at a temperature above 20 ° C and below 80 ° C, temperatures between 30 and 60 ° C being preferred.
  • the contacting of the metal surface with the bath can be carried out in any suitable manner, for example by immersion.
  • the contact time of the surface to be polished with the bath must be sufficient to achieve effective polishing of the surface; however, it cannot exceed a critical value beyond which local corrosions may appear on the surface.
  • the optimum contact time depends on many parameters such as the metal or alloy constituting the surface to be polished, the configuration and initial roughness thereof, the composition of the bath, the working temperature, the possible turbulence of the bath. in contact with the surface, the ratio between the area of the metal surface to be polished and the volume of bath used; it must be determined in each particular case by routine laboratory work.
  • the surface to be polished is kept in contact with the bath for a time sufficient to carry out an attack on the metal to a depth at least equal to 10 microns, preferably between 20 and 50 microns.
  • the duration of the treatment of the surface with the bath is thus, in most cases, between 1 and 5 hours.
  • This bath had a pH value of 2.32.
  • the average depth of attack of the plate was 30 microns.
  • the roughness had fallen to 0.06 microns.
  • Figures 1, 2 and 3 show the profile of the plate surface, respectively, - before polishing, - after the polishing of Example 1, - After the polishing of Example 2.
  • the abscissa scale expresses the length of the surface, in mm and the ordinate scale expresses the relief of the surface, in microns.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
EP88201981A 1987-09-25 1988-09-13 Bäden und Verfahren zum chemischen Polieren von Oberflächen aus Kupfer oder Kupferlegierungen Withdrawn EP0309031A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8713407 1987-09-25
FR8713407A FR2621052A1 (fr) 1987-09-25 1987-09-25 Bains et procede pour le polissage chimique de surfaces en cuivre ou en alliage de cuivre

Publications (1)

Publication Number Publication Date
EP0309031A1 true EP0309031A1 (de) 1989-03-29

Family

ID=9355301

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88201981A Withdrawn EP0309031A1 (de) 1987-09-25 1988-09-13 Bäden und Verfahren zum chemischen Polieren von Oberflächen aus Kupfer oder Kupferlegierungen

Country Status (9)

Country Link
US (1) US4981553A (de)
EP (1) EP0309031A1 (de)
JP (1) JPH01159385A (de)
KR (1) KR890005300A (de)
BR (1) BR8804929A (de)
DK (1) DK529488A (de)
FI (1) FI884332A7 (de)
FR (1) FR2621052A1 (de)
NO (1) NO884228L (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0425012A1 (de) * 1989-10-24 1991-05-02 Solvay Bäder und Verfahren zum chemischen Polieren von Kupfer- oder Kupferlegierung-Oberflächen
WO1992006122A1 (fr) * 1990-10-02 1992-04-16 Interox (Societe Anonyme) Polymeres organophosphoniques et leur utilisation comme stabilisants de solutions aqueuses de peroxyde d'hydrogene

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4026015A1 (de) * 1990-08-17 1992-02-20 Hoechst Ag Verfahren zur herstellung von formkoerpern aus vorstufen oxidischer hochtemperatursupraleiter
US5454876A (en) * 1994-08-02 1995-10-03 21St Century Companies, Inc. Process for reducing lead leachate in brass plumbing components
US5609972A (en) * 1996-03-04 1997-03-11 Polystor Corporation Cell cap assembly having frangible tab disconnect mechanism
US5916453A (en) * 1996-09-20 1999-06-29 Fujitsu Limited Methods of planarizing structures on wafers and substrates by polishing
US6830627B1 (en) 1999-03-23 2004-12-14 International Business Machines Corporation Copper cleaning compositions, processes and products derived therefrom

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1449525A (en) * 1974-08-21 1976-09-15 Tokai Electro Chemical Co Method of stabilizing acid aqueous solutions of hydrogen peroxide
EP0115450A1 (de) * 1983-01-07 1984-08-08 Elf Atochem S.A. Stabilisierung von wässrigen Lösungen,die Wasserstoffperoxid, Fluorwasserstoff und Metallionen enthalten
FR2578261A1 (fr) * 1982-01-11 1986-09-05 Enthone Composition contenant un peroxyde et un oxacide phosphore et procede pour le decapage selectif

Family Cites Families (12)

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US2834659A (en) * 1957-03-25 1958-05-13 Du Pont Chemical polishing of metals
US3345217A (en) * 1964-06-01 1967-10-03 Fremont Ind Inc Method of cleaning and phosphatizing copper circuits
US3779842A (en) * 1972-04-21 1973-12-18 Macdermid Inc Method of and composition for dissolving metallic copper
JPS5221223A (en) * 1975-08-13 1977-02-17 Mitsubishi Gas Chemical Co Chemical polishing solution for copper and its alloy
JPS5265725A (en) * 1975-11-27 1977-05-31 Mitsubishi Gas Chemical Co Method of chemically polishing metals
IT1083401B (it) * 1977-05-27 1985-05-21 Alfachimici Spa Soluzione acida per l'attacco selettivo del rame
US4144119A (en) * 1977-09-30 1979-03-13 Dutkewych Oleh B Etchant and process
US4788086A (en) * 1984-07-14 1988-11-29 Nippondenso Co., Ltd. Copper-based metallic member having a chemical conversion film and method for producing same
SU1211338A1 (ru) * 1984-07-18 1986-02-15 Ордена Трудового Красного Знамени Институт Органической И Физической Химии Им.А.Е.Арбузова Раствор дл химического полировани меди и ее сплавов
JPS61124585A (ja) * 1984-11-21 1986-06-12 Kosaku:Kk プリント基板製造用銅エツチング液の濃度管理法
JPS62237447A (ja) * 1986-04-08 1987-10-17 Mitsubishi Paper Mills Ltd 一液型エツチングブリ−チ液
DE3623504A1 (de) * 1986-07-09 1988-01-21 Schering Ag Kupferaetzloesungen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1449525A (en) * 1974-08-21 1976-09-15 Tokai Electro Chemical Co Method of stabilizing acid aqueous solutions of hydrogen peroxide
FR2578261A1 (fr) * 1982-01-11 1986-09-05 Enthone Composition contenant un peroxyde et un oxacide phosphore et procede pour le decapage selectif
EP0115450A1 (de) * 1983-01-07 1984-08-08 Elf Atochem S.A. Stabilisierung von wässrigen Lösungen,die Wasserstoffperoxid, Fluorwasserstoff und Metallionen enthalten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SOVIET INVENTIONS ILLUSTRATED, vol. 6, no. 8639, 9 octobre 1986, résumé no. 86-257473/39, Derwent Publications Ltd, Londres, GB; & SU-A-12 11 338 (ORG. PHYS. CHEM. INST.) 15-02-1986 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0425012A1 (de) * 1989-10-24 1991-05-02 Solvay Bäder und Verfahren zum chemischen Polieren von Kupfer- oder Kupferlegierung-Oberflächen
US5098517A (en) * 1989-10-24 1992-03-24 Solvay & Cie (Societe Anonyme) Baths and process for chemical polishing of copper or copper alloy surfaces
BE1003761A3 (fr) * 1989-10-24 1992-06-09 Solvay Bains et procede pour le polissage chimique de surfaces en cuivre ou en alliage de cuivre.
WO1992006122A1 (fr) * 1990-10-02 1992-04-16 Interox (Societe Anonyme) Polymeres organophosphoniques et leur utilisation comme stabilisants de solutions aqueuses de peroxyde d'hydrogene
BE1003944A3 (fr) * 1990-10-02 1992-07-22 Interox Sa Polymeres organophosphoniques et leur utilisation comme stabilisants de solutions aqueuses de peroxyde d'hydrogene.

Also Published As

Publication number Publication date
DK529488A (da) 1989-03-26
JPH01159385A (ja) 1989-06-22
KR890005300A (ko) 1989-05-13
DK529488D0 (da) 1988-09-23
US4981553A (en) 1991-01-01
NO884228L (no) 1989-03-28
NO884228D0 (no) 1988-09-23
FI884332A0 (fi) 1988-09-21
FR2621052A1 (fr) 1989-03-31
FI884332L (fi) 1989-03-26
FI884332A7 (fi) 1989-03-26
BR8804929A (pt) 1989-05-02

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