EP0192310B1 - Verfahren und Vorrichtung zum kontinuierlichen Regenerieren eines stromlosen Metallisierungsbades - Google Patents

Verfahren und Vorrichtung zum kontinuierlichen Regenerieren eines stromlosen Metallisierungsbades Download PDF

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Publication number
EP0192310B1
EP0192310B1 EP86200247A EP86200247A EP0192310B1 EP 0192310 B1 EP0192310 B1 EP 0192310B1 EP 86200247 A EP86200247 A EP 86200247A EP 86200247 A EP86200247 A EP 86200247A EP 0192310 B1 EP0192310 B1 EP 0192310B1
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EP
European Patent Office
Prior art keywords
copper
reverse osmosis
electroless
plating bath
plating
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
EP86200247A
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English (en)
French (fr)
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EP0192310A1 (de
Inventor
Eltjo Scholtens
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Koninklijke Philips NV
Original Assignee
Philips Gloeilampenfabrieken NV
Koninklijke Philips Electronics NV
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Publication of EP0192310A1 publication Critical patent/EP0192310A1/de
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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
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1617—Purification and regeneration of coating baths

Definitions

  • the invention relates to a method of continuously regenerating an electroless-plating bath.
  • the invention relates more specifically to a method of continuously regenerating an electroless copper-plating bath.
  • the invention also relates to an electroless-plating device having means for continuously regenerating the electroless-plating bath, which device comprises a treating tank and a dosing device for the bath components consumed in the electroless-plating process.
  • Selectivity is to be understood to mean herein that metal compounds and bath components which do not have to be supplemented are not removed from the bath.
  • Reproducibility is to be understood to mean herein that in time metal layers of constant quality and composition can be deposited independently of the amount of products to be plated per unit of time, however, within the limits dictated by the permissible bath loading.
  • the object of providing a method of continuously regenerating an electroless-plating bath in which a solution which comprises at least metal ions, a reducing agent and a complexing agent for the metal ions is used for electroless-plating is achieved in accordance with the invention by means of a method which is characterized in that consumed components are added to the plating bath and that a part of the bath is neutralized, the neutralized solution being treated by reverse osmosis for removing by-products, whereby a concentrate is produced and returned to the plating bath.
  • United States Patent Specification US 3,637,467 discloses a method in which reverse osmosis is used in a galvanic plating process, however, said process is an electro deposition process in which no waste products need be removed.
  • reverse osmosis is employed to recover bath components from a rinsing bath by concentrating them. Since the filtrate is reused also, the selectivity of the filter is not very important.
  • the method of the invention can vary advantageously be used for the continuous regeneration of an electroless copper-plating bath, the method being characterized in that the metal ions are copper ions and that the solution also comprises an alkali metal hydroxide and one or more surfactants.
  • the method in accordance with the invention is preferably carried out so that reverse osmosis yields a retention of at least 90% of the complexated copper ions and complexing agents.
  • Surfactants which are difficult to analyse must also exhibit the greatest possible retention.
  • the reducing agent for copper ions this group of compounds, which is present in the concentrate of the reverse osmosis device, comprises both the bath components whose amounts remain practically unchanged and the ones which are consumed in and during the electroless copper-plating process. Consequently, the reducing agent, for example, formaldehyde, must be additionally supplied to the copper-plating bath. The reason for this is that there are no suitable filter membranes having a high retention for small organic molecules or ions.
  • the permeate formed in the reverse osmosis process mainly comprises waste products and the reducing agent.
  • the retention value of the waste products should not be too high and is preferably less than 50%.
  • the concentrate produced after reverse osmosis comprises complexated copper ions, the complexing agent and surfactants, and the permeate comprises monovalent anions. Both the concentrate and the permeate comprise alkali-metal ions.
  • the solution which is fed to the reverse osmosis device is neutralized by adding an acid, that the salt thus formed is removed from the concentrate in the reverse osmosis process and that an amount of alkali-metal hydroxide is added to the copper-plating bath exceeding the amount consumed, so as to impart the required acidity to the copper-plating bath.
  • the copper ions to be added to the electroless copper-plating bath to replace the ones consumed in the electroless copper-plating process are added in the form of copper (II) nitrate and the acid employed for neutralizing the solution prior to reverse osmosis is nitric acid.
  • Another object of the invention is to provide a device for carrying out the method described above.
  • a device as described in the opening paragraph which additionally comprises a neutralizing tank, a high-pressure pump and a reverse osmosis device, where the treating tank is connected to the neutralizing tank via an outlet and a pump, where the neutralizing tank, which comprises a dosing device for an acid, is connected to the treating tank by means of an outlet, where the neutralizing tank is connected to the inlet of the reverse osmosis device via an outlet and the high-pressure pump, and the outlet for the concentrate of the reverse osmosis device is connected to the neutralizing tank by means of a pressure valve.
  • An alternative embodiment of the device in accordance with the invention is characterized in that a cooling device is interposed between the neutralizing tank and the high-pressure pump. In both cases, the cooling device is arranged at a location where the liquid to be cooled is not at a high pressure.
  • a special embodiment of the electroless copper-plating device in accordance with the invention is characterized in that the plating bath is a copper-plating bath and that the reverse osmosis device comprises a membrane of cellulose acetate.
  • Figure 1 is a schematic representation of a device in accordance with the invention.
  • Figure 1 shows a treating tank 1 which is filled with a solution for the electroless deposition of metal layers on a substrate, for example, in the form of uniform layers or patterns as in the manufacture of printed circuit boards by means of a fully additive method.
  • a solution for the electroless deposition of metal layers on a substrate for example, in the form of uniform layers or patterns as in the manufacture of printed circuit boards by means of a fully additive method.
  • the substrates which are activated in a known manner are immersed in the solution.
  • the consumed bath components are supplied to the bath by means of a dosing device 2.
  • Part of the solution can be transferred from treating tank 1 to a neutralizing tank 5 by means of a drain 3 and a pump 4.
  • Neutralizing tank 5 comprises an overflow 7 to treating tank 1 and a dosing device 6 for adding an acid.
  • Neutralizing tank 5 is connected to the inlet of a reverse osmosis device 10 by means of a drain 8 and a high-pressure pump 9.
  • the concentrate is led from reverse osmosis device 10 to neutralizing tank 5 via a drain 11, a pressure valve 12 and a cooler 14.
  • the permeate is discharged from reverse osmosis device 10 via an outlet 13, for example, for further processing or storage.
  • cooling device 14 is located between the outlet for the concentrate of the reverse osmosis device 10 and neutralizing tank 5, however, it can also be located between neutralizing tank 5 and the inlet of reverse osmosis device 10.
  • treating tank 1 and neutralizing tank 5 comprise measuring devices 15, for example, for measuring the temperature and the pH-value.
  • measuring devices 15 for example, for measuring the temperature and the pH-value.
  • control devices and safety devices may be present, for example, for checking liquid flows, concentrations, pressure and liquid levels.
  • a treating tank 1 contains 50 litres of a copper-plating solution which comprises 0.03 M of copper (II)-nitrate, 0.05 M of the tetra sodium salt of ethylene diamine tetra-acetic acid (EDTA), 0.05 M of sodium hydroxide and 0.06 M of formaldehyde.
  • EDTA is a complexing agent for copper ions and it is used to prevent the formation of copper (II)-hydroxide in the basic medium and to improve the quality of the copper layers to be formed. Furthermore, complexing prevents the copper ions from being removed from the solution during the reverse osmosis process.
  • Other complexing agents such as ethylene diamine tetra isopropanol, are also suitable for use in the method of the invention.
  • an amount of salt is formed which consists predominantly of sodium nitrate and sodium formate. If the method in accordance with the invention is used, for example, a steady state is achieved in which the salt content lies between 0.4 and 0.8 M. This is an acceptable level, the values at the lower end of the range yielding the best results as to the quality of the copper layers.
  • the solution also comprises surfactants which serve to influence the quality of the deposited copper layers, for example, as to ductility, selectivity, tensile strength, (re-) solderability and smoothness. These surfactants are hardly consumed in the copper-plating process.
  • a suitable surface-active additive is formed by, for example, the combination of 0.1 % by weight of a wetting agent, such as Triton QS-44 ⁇ of Rohm and Haas (a phosphate ester of an alkylaryl polyether alcohol having a molecular weight of approximately 800) and 0.02% by weight of a thioether-polyoxyalkylene compound having the following structural formula: in which m has an average value of 12, (a+c) has an average value of 369 and b has an average value of 55.
  • a wetting agent such as Triton QS-44 ⁇ of Rohm and Haas (a phosphate ester of an alkylaryl polyether alcohol having a molecular weight of approximately 800)
  • a thioether-polyoxyalkylene compound having the following structural formula: in which m has an average value of 12, (a+c) has an average value of 369 and b has an average value of 55.
  • Said compound has the additional advantage that it slightly raises all
  • Oxygen or air is led through the solution so that it contains between 3 and 5 ppm of oxygen.
  • the solution has a pH-value between 11 and 12 and it is used at a temperature of 70°C, the deposition rate being between 2 and 3 urn of copper per hour.
  • the consumed components CU2+, CH 2 0 and HO- are supplemented to the solution in an amount which depends predominantly on the amount of copper produced.
  • the components are supplemented in the form of aqueous solutions of copper (II) nitrate, formaldehyde and sodium hydroxide.
  • the by-products formed in this process predominantly formate and carbonate and the increasing amount of sodium ions and nitrate ions, must be removed from the solution in order to prevent the quality of the deposited layers from deteriorating and to preclude a decrease in selectivity of the copper-plating reaction.
  • the copper ions are present mainly as complexes comprising EDTA and the sodium ions as EDTA salt.
  • the methanol formed in the Canizzarro reaction largely evaporates.
  • part of the copper-plating solution (1-3 I/hr) is fed to a neutralizing tank 5 having a volume of 10 I.
  • Such an amount of 2 M nitric acid is added to the solution in the neutralizing tank that the pH-value is less than 8, preferably, approximately 7.
  • the pH-value is less than 8, preferably, approximately 7.
  • the carbonate ions are then converted into monovalent bicarbonate anions.
  • the solution in the neutralizing tank has a maximum temperature of 30°C, which is achieved by cooling the solution in the reverse osmosis circuit.
  • Part of the solution in the neutralizing tank 5 is fed back to the treating tank 1 by means of an overflow 7.
  • an additional amount of sodium hydroxide is added to the copper-plating solution in the treating tank.
  • the wetting agent used must also be partly supplemented.
  • the neutralized solution (200-300 I/hr) is fed under high pressure (3-4 MPa) to the inlet of a reverse osmosis device 10 which comprises cellulose-acetate membranes having a filter surface area of 0.036 m 2.
  • a reverse osmosis device 10 which comprises cellulose-acetate membranes having a filter surface area of 0.036 m 2.
  • Suitable types of membranes are DDS No. 865 of The Danish Sugar Corporation.
  • Membranes of ceramic aluminium oxide or of porous glass are also suitable.
  • the retention factor is the complement of that fraction of the concentration of a component in the inlet stream, which is still present in the permeate.
  • the retention factor of formaldehyde is almost nil, which means that the concentration of formaldehyde in the permeate (and hence in the concentrate) is almost equal to the concentration in the inlet stream.
  • the retention factor of bicarbonate ions, formate ions and nitrate ions ranges from 0.05 to 0.25.
  • the retention factor of EDTA and Cu-EDTA-. complexes is high: 0.90 and more.
  • the cations in the permeate are almost exclusively sodium ions.
  • the volume flow of the permeate is approximately 1-2 I/hr.
  • the concentrate is returned to neutralizing tank 5 via a pressure valve 12 (which brings the concentrate to atmospheric pressure) and a cooler 14.
  • a pressure valve 12 which brings the concentrate to atmospheric pressure
  • a cooler 14 In order to reduce the amount of salt formed by neutralization, the circulation rate in the circuit of the neutralizing tank and of the reverse osmosis device is chosen to be higher than that in the circuit of the treating tank and of the neutralizing tank. Consequently, the suppletion of sodium hydroxide can be kept at a low level. Polarization and contamination of the membrane is avoided by the high circulation rate through the reverse osmosis device. Polarization occurs where the reverse osmosis process is rendered ineffective due to reduction of the difference in concentration on both sides of the membrane.
  • the method in accordance with the invention has a number of special advantages.
  • the use of a continuous method brings about a steady state which leads to copper layers of constant quality.
  • the process can easily be controlled by controlling the various liquid flows and the size of the (adjustable) membrane surface area. After a change in the process a new steady state will be established automatically.
  • the pH-value of the copper-plating bath can be adjusted and maintained within wide limits.
  • a high selectivity of the copper-plating process (for copper-plating in a pattern) is achieved at a relatively low pH-value, at a higher pH-value, however, the deposition rate of the copper increases.
  • the amounts necessary for supplementation can simply be calculated from the selected copper- production rate, allowing for the side-reactions, and may be verified by analyzing the bath composition.
  • An additional advantage is that components whose amounts are difficult to determine, especially the thioether polyoxyalkylene compound, are hardly consumed and are not discharged, consequently, the concentration of these components can be kept constant without any problems.
  • the wetting agent which has a retention factor of approximately 85%, can be analysed and supplemented relatively easily.
  • copper (II) nitrate is preferably used for supplying copper ions.
  • Copper (II) sulphate which is more commonly used in the art, cannot be used in this method due to the high retention factor of the bivalent sulphate anions. Solutions comprising cyanide have the disadvantage that the cyanide comes into the permeate, thus rendering further processing of the waste problematic.
  • the copper-plating solution is neutralized by means of nitric-acid because this does not result in any new types of anions being added and because the salt formed is removed by reverse osmosis.
  • Other acids having monovalent anions may also be useful, but they have their restrictions.
  • the use of hydrochloric acid may lead to, for example, an unacceptably high iron content in the copper-plating solution due to corrosion of the stainless steel component parts and pipes of the reverse osmosis device.
  • a solution comprising nickel chloride is used for the electroless nickel-plating process, as described in US Patent Specification 3,946,126.
  • the solution is continuously regenerated by means of reverse osmosis.
  • the borate anion formed in the nickel-plating reaction is then removed from the solution but the nickel ions are retained in the form of a pyrophosphate complex and they are fed back to the nickel-plating bath.
  • the method and the device in accordance with the invention may also be used for continuously regenerating plating baths for the electroless deposition of, for example, tin, silver and gold/copper alloys.
  • the retention factor of the metal ions must then be higher, (as close to 1 as possible) than that of the by-products.
  • a continuous regeneration of a plating bath by means of reverse osmosis is then possible by an appropriate choice of the counterions and the use of complexing agents and surfactants in the bath.

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  • 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)
  • Separation Using Semi-Permeable Membranes (AREA)

Claims (10)

1. Verfahren zum kontinuierlichen Regenerieren eines stromlosen Metallisierungsbades, wobei eine Lösung mit wenigstens Metallionen, einem Reduktionsmittel und einem Komplexierungsmittel für die Metallionen zum stromlosen Metallisieren verwendet wird, dadurch gekennzeichnet, daß verbrauchte Bestandteile zu dem Metallisierungsbad hinzugefügt werden und daß ein Teil des Bades neutralisiert wird, wobei zum Entfernen von Nebenprodukten die Neutralisierungslösung durch umgekehrte Osmose behandelt wird, wodurch ein Konzentrat erzeugt und zum Metallisierungsbad zurückgeführt wird.
2. Verfahren nach Anspruch 1, zum kontinuierlichen Regenerieren eines stromlosen Verkupferungsbades, dadurch gekennzeichnet, daß die Metallionen Kupferionen sind und daß die Lösung ebenfalls ein Alkalimetallhydroxid sowie ein oder mehrere oberflächenaktive Mittel aufweist.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die umgekehrte Osmose eine Retention von mindestens 90% der komplexierten Kupferionen und komplexierten Mittel ergibt.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß nach der umgekehrten Osmose das erzeugte Konzentrat komplexierte Kupferionen, das Komplexierungsmittel und oberflächenaktive Mittel enthält und daß das Permeat einweertige Anionen aufweist.
5. Verfahren nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, daß die der Vorrichtung zur umgekehrten Osmose zugeführte Lösung durch Zusatz einer Säure neutralisiert wird, daß das dabei gebildete Salz aus dem erzeugten Konzentrat im umgekehrten Osmoseprozeß entfernt wird und daß dem Verkupferungsbad außer der verbrauchten Menge eine zusätzliche Menge Alkalimetallhydroxid hinzugefügt wird, damit das Verkupferungsbad den gewünschten Säuregrad erhält.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Kupferionen, die dem stromlosen Verkupferungsbad zur Ergänzung der beim stromlosen Verkupfern verbrauchten Kupferionen zugefügt werden, in Form von Kupfer-(II)-Nitrat hinzugefügt werden, und daß die Säure, die zum Neutralisieren der Lösung verwendet wird, vor der umgekehrten Osmose, Salpetersäure ist.
7. Vorrichtung zum stromlosen Metallisieren zum Durchführen des Verfahrens nach einem der Ansprüche 1 bis 6, mit Mitteln zum kontinuierlichen Regenerieren des stromlosen Metallisierungsbades, wobei diese Vorrichtung einen Behandlungsbehälter aufweist sowie eine Dosierungsvorrichtung für die beim stromlosen Metallisieren verbrauchten Badbestandteile, dadurch gekennzeichnet, daß die Vorrichtung außerdem einen Neutralisierungsbehälter, eine Hochdruckpumpe und eine Vorrichtung zum Durchführen der umgekehrten Osmose aufweist, wobei der Behandlungsbehäler über einen Abfluß und eine Pumpe mit dem Neutralisierungsbehälter verbunden ist und wobei der Neutralisierungsbehälter, der die Dosierungsvorrichtung für eine Säure aufweist, mittels eines Abflußes mit dem Behandlungsbehälter verbunden ist und wobei der Neutralisierungsbehälter über einen Abfluß und die Hochdruckpumpe mit dem Eingang der Vorrichtung zum Durchführen der umgekehrten Osmose verbunden ist, und wobei der Abfluß für das Konzentrat der Vorrichtung für umgekehrte Osmose mittels eines Druckventils mit dem Neutralisierungsbehälter verbunden ist.
8. Vorrichtung nach Anspruch 7, dadurch gekennzeichnet, daß zwischen dem Druckventil und dem Neutralisierungsbehälter eine Kühlvorrichtung vorgesehen ist.
9. Vorrichtung nach Anspruch 7, dadurch gekennzeichnet, daß zwischen dem Neutralisierungsbehälter und der Hochdruckpumpe eine Kühlvorrichtung vorgesehen ist.
10. Vorrichtung nach einem der Ansprüche 7 bis 9 zum stromlosen Verkupfern, dadurch gekennzeichnet, daß das Metallisierungsbad ein Verkupferungsbad ist und daß die Vorrichtung für umgekehrte Osmose eine Membran aus Zelluloseacetat aufweist.
EP86200247A 1985-02-20 1986-02-19 Verfahren und Vorrichtung zum kontinuierlichen Regenerieren eines stromlosen Metallisierungsbades Expired - Lifetime EP0192310B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8500474 1985-02-20
NL8500474A NL8500474A (nl) 1985-02-20 1985-02-20 Werkwijze voor het continu regenereren van een stroomloos metalliseringsbad en inrichting voor toepassing van de werkwijze.

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EP0192310A1 EP0192310A1 (de) 1986-08-27
EP0192310B1 true EP0192310B1 (de) 1990-08-22

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EP86200247A Expired - Lifetime EP0192310B1 (de) 1985-02-20 1986-02-19 Verfahren und Vorrichtung zum kontinuierlichen Regenerieren eines stromlosen Metallisierungsbades

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EP (1) EP0192310B1 (de)
JP (1) JPS61194182A (de)
DE (1) DE3673536D1 (de)
NL (1) NL8500474A (de)

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Publication number Priority date Publication date Assignee Title
JPH0653253B2 (ja) * 1986-11-08 1994-07-20 松下電工株式会社 セラミツク基板の粗化法
US4834886A (en) * 1987-01-08 1989-05-30 Filmtec Corporation Process for making alkali resistant hyperfiltration membrane and resulting product
US5328616A (en) * 1992-11-20 1994-07-12 Monsanto Company Methods and apparatus for treating electroless plating baths
US6569307B2 (en) * 2000-10-20 2003-05-27 The Boc Group, Inc. Object plating method and system
CN109609933A (zh) * 2019-02-19 2019-04-12 深圳市天熙科技开发有限公司 一种胶体钯活化液在线净化再生装置

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3022962A1 (de) * 1979-06-19 1981-02-12 Hitachi Ltd Verfahren zum regenerieren einer chemischen verkupferungsloesung

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US3973987A (en) * 1974-03-18 1976-08-10 Data General Corporation Water recycle treatment system for use in metal processing

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3022962A1 (de) * 1979-06-19 1981-02-12 Hitachi Ltd Verfahren zum regenerieren einer chemischen verkupferungsloesung

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EP0192310A1 (de) 1986-08-27
DE3673536D1 (de) 1990-09-27
NL8500474A (nl) 1986-09-16
JPS61194182A (ja) 1986-08-28

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