EP0137397B1 - Bain pour le dépôt galvanique de cuivre et procédé pour sa préparation - Google Patents

Bain pour le dépôt galvanique de cuivre et procédé pour sa préparation Download PDF

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Publication number
EP0137397B1
EP0137397B1 EP84111402A EP84111402A EP0137397B1 EP 0137397 B1 EP0137397 B1 EP 0137397B1 EP 84111402 A EP84111402 A EP 84111402A EP 84111402 A EP84111402 A EP 84111402A EP 0137397 B1 EP0137397 B1 EP 0137397B1
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EP
European Patent Office
Prior art keywords
copper
bath
propane derivatives
bifunctional
polymers derived
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
EP84111402A
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German (de)
English (en)
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EP0137397A3 (en
EP0137397A2 (fr
Inventor
Herbert Iwan
Manfred Schmitz
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.)
Blasberg-Oberflachentechnik GmbH
Original Assignee
Blasberg-Oberflachentechnik GmbH
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Publication of EP0137397A2 publication Critical patent/EP0137397A2/fr
Publication of EP0137397A3 publication Critical patent/EP0137397A3/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the present invention relates to an aqueous acidic galvanic copper bath for the deposition of fine-grained ductile copper containing polymers from bifunctional propane derivatives and, if appropriate, other bath additives, and to the process for producing the same.
  • DE-PS 9 75 247 DE-AS 1 086 508, DE-AS 1 921 845 and DE-AS 2 003 539.
  • DE-AS 1 521 061 also discloses copper baths with to produce a content of polymers, a 1,3-dioxolane polymer having terminal hydroxyl groups being described as the polymer.
  • the copper baths according to DE-OS 15 21 062 can also contain other polyether polymers.
  • the object of the invention is therefore to develop an acidic galvanic copper strip which, apart from an improved scattering capacity, provides fine crystalline, ductile copper deposits, with high elongation at break values and better shock test behavior.
  • an acidic galvanic copper bath for the deposition of fine-grained ductile copper containing polymers from bifunctional propane derivatives and optionally other bath additives characterized in that it contains bifunctional propane derivatives of the formulas 1 and / or II, where X and Y represents a hydroxyl group or halogen, X is not Y and Z is oxygen, sulfur or a methylene group, which were polymerized in the presence of 1 to 50 mol% of one or more unsaturated alcohols having 3 to 10 carbon atoms and one or more double and / or triple bonds at a temperature of 100 to 260 ° C.
  • the molar ratio of polymers from bifunctional propane derivatives to alcohol should be in the range from 2: 1 to 100: 1, preferably 10: 1 to 80: 1.
  • the present invention furthermore relates to a process for the preparation of an acidic galvanic copper bath for the deposition of fine-grained ductile copper containing polymers from bifunctional propane derivatives and, if appropriate, other bath additives, characterized in that the bifunctional propane derivatives are present in the presence of 1 to 50 mol%. polymerizes one or more unsaturated alcohols with 3 to 10 carbon atoms and one or more double and / or triple bonds, dilutes the polymer at temperatures below 100 ° C. with water and optionally small amounts of a lower alcohol and then adds it to the acidic copper bath.
  • Typical examples of these substances are monochlorohydrin, epichlorohydrin and glycid (glycidol).
  • the bifunctional propane derivatives can be polymerized in a manner known per se by adding catalysts such as protonic acids and Lewis acids.
  • catalysts such as protonic acids and Lewis acids.
  • Boron trifluoride etherate has proven particularly useful as Lewis acid, but other catalysts are also suitable for the preparation of the polymers used according to the invention.
  • the polymers used according to the invention are copolymers of the bifunctional propane derivatives, the end groups of which contain unsaturated alcohols.
  • Polymers of glycides include poly ethers with primary or secondary OH groups as well as terminal groups belonging to an unsaturated alcohol. These polymers are viscous in their pure form and can be dissolved in hot water or in hot water with the addition of lower alcohols. They are added to the copper bath in the form of such aqueous or aqueous-alcoholic solutions. If necessary, the undissolved material is filtered off beforehand.
  • the amount of additive according to the invention is not critical. It has been shown that amounts of 0.1 to 1 g of polymer per liter of copper bath are completely sufficient to achieve the desired effect. If the solutions of the polymer are adjusted to a concentration of approximately 2.5% by weight, 4 to 40 ml of this solution per liter of copper bath are sufficient.
  • the copper baths according to the invention can be used at current densities between 0.5 and 10 Aldm2.
  • the copper plating of conductor tracks shows that layer thicknesses are also achieved in the boreholes which are over 90% of the thickness of the layer thicknesses otherwise achieved.
  • circuit boards produced with the copper bath according to the invention with copper coatings of 20 to 30 ⁇ m are subjected to a temperature shock test by heating to 250 ° C. in an oil bath and then cooling again to room temperature, no defects and edge breaks in the copper layer are observed even after 10 cycles .
  • Copper foils of 50 ⁇ m thickness produced with the aid of the copper bath according to the invention show measured values in the range from 6 to 20% in the test for elongation at break.
  • Another advantage of the copper baths according to the invention is that instead of the usual concentration of 10 to 20 g / l copper and 100 to 250 g / l sulfuric acid, now also at concentrations of 40 to 80 g / l copper and 30 to 80 g / l Sulfuric acid can work.
  • the copper baths according to the invention can be moved in the usual way by blowing in air.
  • the bath temperature is generally 15 to 40 ° C.
  • cathodic current densities of 0.5-4 A / dm 2 finely crystalline, ductile copper coatings with excellent scattering capacity are deposited from this electrolyte. If a circuit board with a material thickness of 3 mm and a bore diameter of 0.3 mm is copper-plated in the electrolytes according to the invention, cathodic current densities of 0.5-1.0 Aldm 2 in the holes layer thicknesses of over 90% based on the conductor track.
  • the elongation at break is determined on copper foils (50 .mu.m) produced in the electrolyte according to the invention, measurement values in the range of 6-20% are obtained. It is essential that the elongation at break values remain constant even after a long period of operation of the electrolyte, that is to say that no disruptive degradation products are formed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (4)

1. Bain acide de cuivrage galvanique pour le dépôt de cuivre ductile à grain fin, contenant des polymères issus de dérivés bifonctionnels du propane et, le cas échéant, d'autres additifs de bain, caractérisé en ce qu'il contient de dérivés bifonctionnels du propane répondant aux formules 1 et/ou Il dans lesquelles X est différent de Y et Z représente l'oxygène, le soufre ou un groupe méthylène
Figure imgb0008
Figure imgb0009
qui ont été polymérisées en présence de 1 à 50 moles % d'un alcool ou de plusieurs alcools insaturés ayant 3 à 10 atomes de carbone et une ou plusieurs doubles et/ou triples liaisons, à une température comprise entre 100 et 260°C.
2. Bain selon la revendication 1, caractérisé en ce que le rapport molaire entre les produits de polymérisation issus de dérivés bifonctionnels du propane et l'alcool est compris entre 2:1 et 100:1.
3. Bain selon l'une des revendications 1 ou 2, caractérisé en ce que le rapport molaire entre les produits de polymérisation issus de dérivés de propane bifonctionnels et l'alcool est compris entre 10:1 et 80:1.
4. Procédé de préparation d'un bain de cuivrage acide galvanique pour le dépôt de cuivre ductile à grain fin, contenant des polyméres issus de dérivés bifonctionnels du propane selon la revendication 1 et, le cas échéant, d'autres additifs de bain, caractérisé en ce que les dérivés bifonctionnels du propane sont polymérisés en présence de 1 à 50 moles % d'un ou de plusieurs alcools insaturés ayant 3 à 10 atomes de carbone et une ou plusieurs doubles et/ou triples liaisons, le produit de polymérisation étant ensuite dilué avec de l'eau à des températures inférieures à 100°C et, au besoin, avec de petites quantités d'un alcool inférieur, puis aouté au bain acide de cuivrage.
EP84111402A 1983-09-28 1984-09-25 Bain pour le dépôt galvanique de cuivre et procédé pour sa préparation Expired - Lifetime EP0137397B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3335079 1983-09-28
DE3335079 1983-09-28

Publications (3)

Publication Number Publication Date
EP0137397A2 EP0137397A2 (fr) 1985-04-17
EP0137397A3 EP0137397A3 (en) 1988-02-17
EP0137397B1 true EP0137397B1 (fr) 1990-08-29

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EP84111402A Expired - Lifetime EP0137397B1 (fr) 1983-09-28 1984-09-25 Bain pour le dépôt galvanique de cuivre et procédé pour sa préparation

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EP (1) EP0137397B1 (fr)
DE (1) DE3483078D1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4338148C2 (de) * 1993-11-04 1997-01-30 Atotech Deutschland Gmbh Verfahren zur elektrolytischen Abscheidung matter und pickelfreier Kupferschichten mit hoher Bruchdehnung auf Substratoberflächen
KR100545664B1 (ko) 1998-05-16 2006-01-24 블라스베르그 오베르플래켄테크닉 게엠베하 기판의 구리 도금 방법
JP3899313B2 (ja) * 2000-10-19 2007-03-28 アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング 銅浴および無光沢銅被膜の電着方法
DE10058896C1 (de) * 2000-10-19 2002-06-13 Atotech Deutschland Gmbh Elektrolytisches Kupferbad, dessen Verwendung und Verfahren zur Abscheidung einer matten Kupferschicht

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DE3483078D1 (de) 1990-10-04
EP0137397A3 (en) 1988-02-17
EP0137397A2 (fr) 1985-04-17

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