EP0425012B1 - Bäder und Verfahren zum chemischen Polieren von Kupfer- oder Kupferlegierung-Oberflächen - Google Patents

Bäder und Verfahren zum chemischen Polieren von Kupfer- oder Kupferlegierung-Oberflächen Download PDF

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Publication number
EP0425012B1
EP0425012B1 EP90202734A EP90202734A EP0425012B1 EP 0425012 B1 EP0425012 B1 EP 0425012B1 EP 90202734 A EP90202734 A EP 90202734A EP 90202734 A EP90202734 A EP 90202734A EP 0425012 B1 EP0425012 B1 EP 0425012B1
Authority
EP
European Patent Office
Prior art keywords
baths
bath
ions
polishing
copper
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.)
Expired - Lifetime
Application number
EP90202734A
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English (en)
French (fr)
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EP0425012A1 (de
Inventor
Daniel Tytgat
Stéfaan 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
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Solvay SA
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Filing date
Publication date
Application filed by Solvay SA filed Critical Solvay SA
Priority to AT90202734T priority Critical patent/ATE88223T1/de
Publication of EP0425012A1 publication Critical patent/EP0425012A1/de
Application granted granted Critical
Publication of EP0425012B1 publication Critical patent/EP0425012B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • 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 present invention relates to 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-dimethylaminomethylphenol [SU -A-1211338 (ORG. PHYS. CHEM. INST.)].
  • These known baths would have the property of better stability, but they imply working temperatures of at least 50 ° C., their speed of action is too fast and they do not allow regular quality polishing.
  • the invention aims to provide another composition for polishing baths which also overcomes the drawbacks listed above and which produce good quality polishes with a slow speed of action and moderate loss of metal.
  • the invention therefore relates to baths for the chemical polishing of copper or copper alloy surfaces, comprising, in aqueous solution, hydrogen peroxide and phosphoric acid according to which they also include tetraborate ions and according to which the amounts of hydrogen peroxide, phosphoric acid and tetraborate ions are respectively between 1 and 5 moles / l, between 0.01 and 1 mole / l and between 0.01 and 0.5 mole / 1, the quantities of phosphoric acid and tetraborate ions being further adjusted to measure in the bath a pH value of less than 3.
  • the hydrogen peroxide serves as an oxidizing agent for the metal to be polished.
  • the phosphoric acid and the tetraborate ions serve as a buffer mixture for the aqueous solution, the pH of which must be acidic.
  • the tetraborate ions can be used in the form of all water-soluble inorganic compounds, such as acid tetraboric or alkali metal salts, for example anhydrous or hydrated borax.
  • the phosphoric acid and the tetraborate ions be present in the aqueous solution in respective amounts adjusted to give the latter a pH value preferably between 1 and 2.8, the optimum values being between 1.4 and 2.5.
  • These pH values are those actually measured in the aqueous solution of the baths according to the invention (apparent pH); they generally differ from the theoretical values obtained by mathematical calculation from the contents of phosphoric acid and tetraborate ions in the aqueous solution.
  • the respective contents of hydrogen peroxide, phosphoric acid and tetraborate ions are chosen according to the nature of the metal treated and the working temperature. and the desired duration for the polishing treatment.
  • the baths comprise, per liter of the aqueous solution, from 1 to 5 moles of hydrogen peroxide, from 0.01 to 1 mole of phosphoric acid and from 0.01 to 0.5 mole of tetraborate ions.
  • aqueous solution of the baths according to the invention may optionally 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 good 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 baths according to the invention lies in their ability to carry out polishing at moderate speed of action, which can be distributed over several hours, so as to allow uniform polishing of large surfaces or surfaces that are difficult to access.
  • the baths according to the invention have the advantageous characteristic of limiting to a moderate value the loss of metal from the metal surfaces subjected to polishing, while producing a polish of quality at least equal and generally superior to the quality of the polish obtained with the baths of known polishing.
  • This feature of the baths according to the invention is intended especially for the treatment of thin metal parts; it also mitigates the loss in mechanical strength of the metal parts subjected to polishing.
  • the baths according to the invention are suitable for polishing all surfaces of copper or copper alloy, for example brass.
  • 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 contact 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.
  • Time to optimum contact 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 the 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 5 microns, preferably less than 50 microns, for example between 5 and 30 microns and, preferably between 10 and 30 microns.
  • the duration of the treatment of the surface with the bath is thus, in most cases, between 1 and 6 hours.
  • the metal surface to be polished is brought into contact successively with a first polishing bath in accordance with the invention and with a second chemical polishing bath comprising, in aqueous solution, hydrogen peroxide, chloride ions and a mixture of phosphate ions and hydrogen phosphate ions in, respective amounts adjusted to give the aqueous solution a pH value between 1.25 and 3.
  • a second chemical polishing bath comprising, in aqueous solution, hydrogen peroxide, chloride ions and a mixture of phosphate ions and hydrogen phosphate ions in, respective amounts adjusted to give the aqueous solution a pH value between 1.25 and 3.
  • the pH value of the bath thus prepared was measured: 2.2.

Landscapes

  • 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)
  • Paper (AREA)
  • Jib Cranes (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Claims (6)

  1. Bäder zum chemischen Polieren von Kupfer- oder Kupferlegierung-Oberflächen, die in wässriger Lösung Wasserstoffperoxyd und Phosphorsäure umfassen, dadurch gekennzeichnet, daß sie auch Tetraborationen umfassen und, daß die Mengen an Wasserstoffperoxyd, Phosphorsäure und Tetraborationen jeweils zwischen 1 und 5 Mol/l, zwischen 0,01 und 1 Mol/l und zwischen 0,01 und 0,5 Mol/l betragen, wobei die jeweiligen Mengen an Phosphorsäure und Tetraborationen außerdem so eingestellt sind, daß man in dem Bad einen pH-Wert kleiner als 3 mißt.
  2. Bäder nach Anspruch 1, dadurch gekennzeichnet, daß die Tetraborationen in der wässrigen Lösung in Form von Alkalimetall-Tetraborat eingesetzt werden.
  3. Bäder nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß sie die Phosphorsäure und die Tetraborationen in so eingestellten Mengen enthalten, daß man in dem Bad einen pH-Wert zwischen 1 und 2,8 mißt.
  4. Verfahren zum Polieren einer Kupfer- oder Kupferlegierung-Oberfläche, gemäß dem man die Oberfläche mit einem chemischen Polierbad gemäß einem der Ansprüche 1 bis 3 in Kontakt bringt.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man die Oberfläche mit dem Bad solange in Kontakt hält, bis ein Angriff des Metalls auf eine Tiefe zwischen 5 und 30 Mikron durchgeführt ist.
  6. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß man die Oberfläche nacheinander mit einem ersten chemischen Polierbad gemäß einem der Ansprüche 1 bis 3 und mit einem zweiten chemischen Polierbad in Kontakt bringt, das, in wässriger Lösung, Wasserstoffperoxyd, Chloridionen, und eine Mischung von Phosphorsäure, Phosphationen und Hydrogenphosphationen in jeweils so eingestellten Mengen umfaßt, um der wässrigen Lösung einen pH-Wert zwischen 1,25 und 3 zu verleihen.
EP90202734A 1989-10-24 1990-10-15 Bäder und Verfahren zum chemischen Polieren von Kupfer- oder Kupferlegierung-Oberflächen Expired - Lifetime EP0425012B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90202734T ATE88223T1 (de) 1989-10-24 1990-10-15 Baeder und verfahren zum chemischen polieren von kupfer- oder kupferlegierung-oberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE8901150 1989-10-24
BE8901150A BE1003761A3 (fr) 1989-10-24 1989-10-24 Bains et procede pour le polissage chimique de surfaces en cuivre ou en alliage de cuivre.

Publications (2)

Publication Number Publication Date
EP0425012A1 EP0425012A1 (de) 1991-05-02
EP0425012B1 true EP0425012B1 (de) 1993-04-14

Family

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Family Applications (1)

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EP90202734A Expired - Lifetime EP0425012B1 (de) 1989-10-24 1990-10-15 Bäder und Verfahren zum chemischen Polieren von Kupfer- oder Kupferlegierung-Oberflächen

Country Status (10)

Country Link
US (1) US5098517A (de)
EP (1) EP0425012B1 (de)
JP (1) JPH03193886A (de)
KR (1) KR910008167A (de)
AT (1) ATE88223T1 (de)
BE (1) BE1003761A3 (de)
CA (1) CA2028195A1 (de)
DE (1) DE69001349D1 (de)
FI (1) FI905229A0 (de)
NO (1) NO904579L (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242542A (en) * 1992-08-17 1993-09-07 Alain Masse Solution and method for removing zinc from the surface of a galvanized metal
US5279707A (en) * 1992-10-23 1994-01-18 Time Savers Die discoloration remover solution and method
DE69329249T2 (de) * 1993-01-11 2001-02-01 Macdermid, Inc. Phosphatisierungsverfahren, insbesondere für die herstellung von leiterplatten und verwendung organischer rückstände
US5630950A (en) * 1993-07-09 1997-05-20 Enthone-Omi, Inc. Copper brightening process and bath
DE4402788A1 (de) * 1994-01-31 1995-08-10 Emil Krechen Industrievertretu Verfahren zum Abtragen von Metallen
US5916453A (en) 1996-09-20 1999-06-29 Fujitsu Limited Methods of planarizing structures on wafers and substrates by polishing
US6858097B2 (en) * 1999-12-30 2005-02-22 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Brightening/passivating metal surfaces without hazard from emissions of oxides of nitrogen
US6368969B1 (en) 2000-06-30 2002-04-09 International Business Machines Corporation Chemical-mechanical polishing methods
US20100062693A1 (en) * 2008-09-05 2010-03-11 Taiwan Semiconductor Manufacturing Co., Ltd. Two step method and apparatus for polishing metal and other films in semiconductor manufacturing
JP6043148B2 (ja) * 2012-10-25 2016-12-14 ユニチカ株式会社 銅エッチング液
CN103849876B (zh) * 2012-12-03 2016-04-06 浙江伟星实业发展股份有限公司 一种化学抛光方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE284558C (de) * 1900-01-01
BE652530A (de) * 1963-09-02
JPS512975A (ja) * 1974-06-28 1976-01-12 Hitachi Ltd Etsuchingueki
GB1449525A (en) * 1974-08-21 1976-09-15 Tokai Electro Chemical Co Method of stabilizing acid aqueous solutions of hydrogen peroxide
IT1083401B (it) * 1977-05-27 1985-05-21 Alfachimici Spa Soluzione acida per l'attacco selettivo del rame
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
FR2621052A1 (fr) * 1987-09-25 1989-03-31 Solvay Bains et procede pour le polissage chimique de surfaces en cuivre ou en alliage de cuivre

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Protection of Metals, vol. 25, no. 2 (mars/avril 1989), page 257; New York, US, A.I.Turashev. *

Also Published As

Publication number Publication date
KR910008167A (ko) 1991-05-30
NO904579D0 (no) 1990-10-23
JPH03193886A (ja) 1991-08-23
US5098517A (en) 1992-03-24
EP0425012A1 (de) 1991-05-02
NO904579L (no) 1991-04-25
DE69001349D1 (de) 1993-05-19
FI905229A0 (fi) 1990-10-24
BE1003761A3 (fr) 1992-06-09
CA2028195A1 (fr) 1991-04-25
ATE88223T1 (de) 1993-04-15

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