EP0088465B1 - Mélange stabilisant pour un bain de cuivrage chimique - Google Patents

Mélange stabilisant pour un bain de cuivrage chimique Download PDF

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Publication number
EP0088465B1
EP0088465B1 EP83200279A EP83200279A EP0088465B1 EP 0088465 B1 EP0088465 B1 EP 0088465B1 EP 83200279 A EP83200279 A EP 83200279A EP 83200279 A EP83200279 A EP 83200279A EP 0088465 B1 EP0088465 B1 EP 0088465B1
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EP
European Patent Office
Prior art keywords
solution according
present
concentration ranging
ppm
copper sulphate
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
Application number
EP83200279A
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German (de)
English (en)
French (fr)
Other versions
EP0088465A1 (fr
Inventor
Francesco Dr. Tomaiuolo
Mauro Bocchino
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.)
Alfachimici SpA
Original Assignee
Alfachimici SpA
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 Alfachimici SpA filed Critical Alfachimici SpA
Publication of EP0088465A1 publication Critical patent/EP0088465A1/fr
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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
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents

Definitions

  • the present invention relates to an aqueous solution for anelectric and autocatalytic copper plating, containing a source of cupric ions, a source of oxhydrylic ions, a reducing agent and a complexing agent in a quantity which makes it possible to maintain the soluble cupric ions in medium. alkaline.
  • Anelectric and autocatalytic copper plating baths are capable of depositing a layer of copper on a catalytic support, without the intervention of an external electron source.
  • these baths consist of aqueous solutions containing a copper salt, a copper complexing agent, a reducing agent and a pH regulator.
  • Copper can be used in the form of sulphate, halide, nitrate, fluoborate, acetate or in the form of other inorganic or even organic salts. In general, for economic reasons, it is preferred to use copper in the form of sulfate pentahydrate.
  • the complexing agent has the function of keeping the copper in solution in the alkaline medium necessary for the deposition reaction.
  • Rochelle salt sodium and potassium tartrate
  • gluconic acid or gluconates nitrilo triacetic acid or its alkaline salts
  • triethanolamine or even complexing agents such as ethylenediaminetetraacetic acid and its sodium salts, N-hydroxyethylethylenediamine-triacetate, N, N, N 1 , N 1 , tetra (2-hydroxy-propyl) -ethylenediamine and others.
  • the copper reducing agent which is normally used in chemical copper baths is formaldehyde or its derivatives or precursors, such as paraformaldehyde, trioxane or the like.
  • Also used as reducing agents are the alkali metal borohydrides, such as sodium borohydride or boranes of the dimethylaminoborane type and others. For this purpose it is also possible to use hypophosphites of alkali metals.
  • the pH regulator has the function of maintaining an optimal degree of alkalinity for the redox reaction which leads to the deposition of a layer of copper on the catalytic support. Normally we work at pH between 10 and 14 and to maintain these pH values we use sodium or potassium hydroxide.
  • chemical copper baths also include a whole series of products present in small concentrations, such as stabilizers, wetting agents, etc.
  • the products which exert a stabilizing action and which are used in the common technique are in general mercury salts, cyanides of alkali metals, organic nitriles or compounds containing sulfur in bivalent form such as 2-mercaptobenzotriazole, thiourea , inorganic sulfides such as alkali metal sulfides or alkali metal thiocyanates or dithionates.
  • These stabilizers are generally catalytic poisons and many of them have the characteristic of greatly reducing the deposition rate or, ultimately, completely blocking the bath, that is to say making it non-autocatalytic.
  • a treatment is generally carried out which has the function of carefully degreasing the surfaces and of conditioning them in order to promote, in the successive phase of catalysis, the adhesion of a thin and uniform layer of noble metal.
  • the catalyst solution which is generally based on palladium chloride and stannous chloride in acid solution with HCl or in saline solution with NaCl or LiCl.
  • This solution contains a palladium and tin compound, present in colloidal form.
  • the acceleration phase which has the function of preventing the transport of coarse particles of catalyst, not adhering to the substrate to be metallized, in the chemical copper plating bath.
  • this acceleration bath has the function of increasing the palladium / tin ratio in the colloidal assembly in order to raise its catalytic capacities.
  • this solution is an acid solution with fluoboric, perchloric acid or the like, or else an alkaline solution with NaOH or the like.
  • the deposit of copper plating without current finds application in the decorative field and in the technique of electro-molding, in which on a plastic support, made conductive by a deposit of chemical copper, is deposited an appropriate thickness of metal which can thus take forms that cannot be obtained by any other working technique.
  • the deposit without current finds all its application in the field of electronics, and particularly in the production of printed circuits with metallized holes.
  • the present invention fits into this field and it is intended to allow optimal stabilization of the bath without thereby adversely affecting its operational characteristics of deposition rate and the physical characteristics of the deposit obtained, such as the gloss and the ductility. .
  • the object of the present invention is to stabilize a bath for anetectric deposition and. autocatalytic of copper using a mixture of stabilizers which, taken as a whole, act synergistically and in a particularly effective way.
  • an aqueous solution for anelectric and autocatalytic copper plating containing a source of cupric ions, a source of oxhydrylic ions, a reducing agent and a complexing agent in an amount making it possible to maintain the cupric ions soluble in alkaline medium, characterized in that it additionally contains a stabilizing mixture constituted by allyl-thiourea, by at least one ferrocyanide of an alkali metal or of ammonium ions and by at least one octylphenyl ether polyethylene oxide with 9-10 moles of ethylene oxide per mole of octylphenol, said three stabilizing compounds manifesting a synergistic action.
  • Allyl-thiourea provides a particularly bright and clear deposit without spots or shadows, unlike thiourea which causes deposition effects and irregular aspects of the surface. Allyl-thiourea effectively develops its action at concentrations between traces and a few milligrams per liter, beyond which, being a catalytic poison like all bivalent sulfur compounds, it would be able to completely block the bath and prevent then the copper deposit.
  • the optimal concentration range is between 0.1 and 2.5 ppm.
  • Ferrocyanide may be present as the salt of alkali metals or ammonium ions but, preferably, as the potassium salt. Ferrocyanide acts in a fairly wide concentration range, which ranges from 100 to 3000 parts per million. The optimal interval so that it concretely takes place the synergistic stabilizing action in cooperation with the other two stabilizers, according to the present invention, is from 500 to 1500 ppm approximately.
  • the third stabilizer in question is an octylphenyl ether of polyethylene oxide with 9-10 moles of ethylene oxide per mole of octylphenol, with an average molecular weight of approximately 650.
  • This product has the trade name of Triton x-100® and it is produced by the Rohm and Haas Co.
  • Triton x-100 is a particularly effective surfactant and it is already used as such in the preparation of baths for deposition copper without electric current.
  • Triton x-100 is used specifically as a stabilizer in conjunction with the two other stabilizers described above, and not for its surface-active action.
  • Triton x-100 can be present in concentrations between 0.1 and 5 g / I; but it takes place an optimal action according to the purpose of the present invention at concentrations between 0.4 and 0.8 g / I. At concentrations below 0.4 g / l the rate of deposition of the bath increases appreciably, but its stability does not give sufficient guarantees. If the limit of 0.8 g / I is exceeded, the deposition rate slows down remarkably without the stability of the bath improving appreciably.
  • Ethylan-20 belongs to the same chemical family of Triton x-100; it is a polyoxyethylene nonionic surfactant and more precisely a polyethylene nonylphenyl ether with approximately 20 moles of ethylene oxide per mole of nonylphenol, and therefore a little heavier and hydrophilic than Triton x -100.
  • the increase in stability deriving from the use of the ternary stabilizing mixture disappears completely, thus confirming that Triton x-100 does not act exclusively as a surfactant and that, however, it cannot be substituted by another. any surfactant.
  • case 8 corresponding to a ternary mixture of allyl-thiourea, potassium ferrocyanide and Triton x-100 0 , is highlighted by the long time required for the accelerated decomposition of the bath containing this mixture.
  • the physical characteristics of the deposits which can be obtained are excellent and, in particular, shine and ductility, as the following example demonstrates.
  • the ductility was determined by detaching the deposit from the glass support and bending it several times by 180 ° while applying a slight pressure each time to flatten the folded edge.
  • the thickness of the deposit was determined by gravimetry, the surface of the plate being known.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
EP83200279A 1982-03-09 1983-02-24 Mélange stabilisant pour un bain de cuivrage chimique Expired EP0088465B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT6727282 1982-03-09
IT67272/82A IT1157006B (it) 1982-03-09 1982-03-09 Miscela stabilizzante per un bagno di rame chimico

Publications (2)

Publication Number Publication Date
EP0088465A1 EP0088465A1 (fr) 1983-09-14
EP0088465B1 true EP0088465B1 (fr) 1986-07-02

Family

ID=11301028

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83200279A Expired EP0088465B1 (fr) 1982-03-09 1983-02-24 Mélange stabilisant pour un bain de cuivrage chimique

Country Status (6)

Country Link
US (1) US4443257A (enrdf_load_stackoverflow)
EP (1) EP0088465B1 (enrdf_load_stackoverflow)
JP (1) JPS58153767A (enrdf_load_stackoverflow)
CA (1) CA1188056A (enrdf_load_stackoverflow)
DE (1) DE3364305D1 (enrdf_load_stackoverflow)
IT (1) IT1157006B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003098681A1 (en) * 2002-05-16 2003-11-27 National University Of Singapore Wafer level electroless copper metallization and bumping process, and plating solutions for semiconductor wafer and microchip

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6070183A (ja) * 1983-09-28 1985-04-20 C Uyemura & Co Ltd 化学銅めっき方法
DE3622090C1 (enrdf_load_stackoverflow) * 1986-07-02 1990-02-15 Blasberg-Oberflaechentechnik Gmbh, 5650 Solingen, De
JP2558209B2 (ja) * 1993-01-22 1996-11-27 日本機械工業株式会社 防雪柵
US6897152B2 (en) * 2003-02-05 2005-05-24 Enthone Inc. Copper bath composition for electroless and/or electrolytic filling of vias and trenches for integrated circuit fabrication
US7750056B1 (en) 2006-10-03 2010-07-06 Sami Daoud Low-density, high r-value translucent nanocrystallites
US10660217B2 (en) * 2017-05-30 2020-05-19 Jun Yang Methods of fast fabrication of single and multilayer circuit with highly conductive interconnections without drilling

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3361580A (en) * 1963-06-18 1968-01-02 Day Company Electroless copper plating
CH490509A (de) * 1966-02-01 1970-05-15 Photocircuits Corporations Bad zum stromlosen Abscheiden von Metallschichten
US3485643A (en) * 1966-05-06 1969-12-23 Photocircuits Corp Electroless copper plating
FR1522048A (fr) * 1966-05-06 1968-04-19 Photocircuits Corp Dépôt non galvanique de métaux
BE757573A (fr) * 1969-10-16 1971-04-15 Philips Nv Depot sans courant de cuivre flexible
US4138267A (en) * 1976-12-28 1979-02-06 Okuno Chemical Industry Company, Limited Compositions for chemical copper plating

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003098681A1 (en) * 2002-05-16 2003-11-27 National University Of Singapore Wafer level electroless copper metallization and bumping process, and plating solutions for semiconductor wafer and microchip

Also Published As

Publication number Publication date
DE3364305D1 (en) 1986-08-07
IT1157006B (it) 1987-02-11
CA1188056A (en) 1985-06-04
IT8267272A0 (it) 1982-03-09
JPS58153767A (ja) 1983-09-12
JPH0237430B2 (enrdf_load_stackoverflow) 1990-08-24
EP0088465A1 (fr) 1983-09-14
US4443257A (en) 1984-04-17

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