EP0036940A1 - Process for the electroless deposition of metals - Google Patents

Process for the electroless deposition of metals Download PDF

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Publication number
EP0036940A1
EP0036940A1 EP81101169A EP81101169A EP0036940A1 EP 0036940 A1 EP0036940 A1 EP 0036940A1 EP 81101169 A EP81101169 A EP 81101169A EP 81101169 A EP81101169 A EP 81101169A EP 0036940 A1 EP0036940 A1 EP 0036940A1
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EP
European Patent Office
Prior art keywords
bath
metal
concentration
deposition
substrate surface
Prior art date
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Granted
Application number
EP81101169A
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German (de)
French (fr)
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EP0036940B1 (en
Inventor
Dieter Dr. Schmitt
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Merck Patent GmbH
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Merck Patent GmbH
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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
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • 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
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • 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
    • C23C18/1633—Process of electroless plating
    • C23C18/1675—Process conditions
    • C23C18/1683—Control of electrolyte composition, e.g. measurement, adjustment
    • 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
    • C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50

Definitions

  • the invention relates to a method for electroless metal deposition.
  • the layer thickness is not always as uniform at all points as is desirable for the economic utilization of the metal salts contained in the baths.
  • two or more sub-baths - one with the metal salt, a second with the necessary reducing agent, optionally further with additives such as complexing agents, stabilizers and / or brightening agents - are sprayed simultaneously but separately in order to separate the metal before it hits it to avoid coating the substrate surface.
  • additives such as complexing agents, stabilizers and / or brightening agents -
  • a macroscopically uniform metal coating is created, which, however, has a granular structure in the micro-range in which the layer thicknesses in neighboring micro-ranges can differ from one another by a multiple.
  • the quality of each metal coating is usually determined by the points with the smallest layer thickness; To achieve an overall satisfactory coating quality, considerably more metal coating bath is therefore used. corresponds to the necessary minimum layer thickness.
  • the amount of metal which is unnecessarily deposited at the locations with a high layer thickness means a considerable loss.
  • the object of the present invention was to provide a method for electroless metal deposition by spraying a metal deposition bath, in which the metal is deposited in a layer thickness that is as uniform as possible.
  • a very uniform metal layer can be produced by spraying an aqueous metal deposition bath onto a substrate surface if the metal deposition bath is diluted with water at the moment it hits the substrate surface.
  • the rate of separation is essentially determined by the concentrations of the reactants in the sprayed droplets that unite. If the concentration is reduced by the addition of water at the moment of impact, the time until the metal deposition begins is longer. During this time, the sprayed-on droplets can be thoroughly mixed so that the metal deposition does not begin in a punctiform manner, but rather in the form of a very thin but closed layer.
  • the same effect is achieved if initially very dilute solutions of the metal salt partial bath and the reducing agent partial bath are sprayed on through separate nozzles to form a well-mixed, highly diluted metal deposition bath.
  • the invention thus relates to the process for the electroless deposition of a uniform metal layer by spraying a metal deposition bath containing a metal salt and a reducing agent and possibly further additives onto a substrate surface, which is characterized in that by reducing the bath concentration, a coherent thin metal coating is first produced on the substrate surface is, which is strengthened by subsequent treatment with a deposition bath of conventional concentration to the desired thickness.
  • the method according to the invention can in principle be used with all metal coatings which are usually deposited without current. Since it enables significant savings on metal salts, it is preferred for the application of precious metal layers, for example made of gold, silver, platinum or palladium.
  • the customary reducing agents can be used for each metal to be deposited by the process according to the invention, for example hypophosphite for gold, formaldehyde, sugar or sugar derivatives for silver, hydrazine hydrate for platinum or palladium.
  • the process according to the invention can be used wherever a conventional aqueous metal deposition bath is sprayed onto a substrate surface.
  • the dilution step according to the invention can be carried out in various ways.
  • the metal deposition bath can be sprayed into a possibly moving thin water layer on the substrate surface, the amount of water being selected such that the concentration of the bath or at least the metal salt sub-bath is 50 to 5 at the moment the spray jet hits the water layer % of the concentration in the spray jet is reduced.
  • the method according to the invention is applied to the metal deposition systems customary in practice, where the substrate is moved on a conveyor belt under a number of spray nozzles arranged one behind the other in the direction of movement of the conveyor belt, the beam with the spray nozzles moving transversely to the direction of movement of the Conveyor belt moved back and forth over the substrate.
  • pure water is sprayed from the first nozzle - as seen in the direction of movement of the conveyor belt - under such a pressure that a water wave forms when it hits the substrate, which, depending on the transport speed of the belt and the spraying agent, has its greatest amplitude runs a short distance in front of the spray cone.
  • the second and possibly further nozzles or pairs of nozzles, from which the metallization bath, optionally also in the form of partial baths, is sprayed, are then set such that their spray cones are partially coexistent. that of the water nozzle overlaps, the center of the spray cone of the second nozzle or pair of nozzles being set approximately above the highest point of the water wave running in front of the first spray cone. However, it may also be expedient to set the spray cone of the water nozzle (s) so that it completely overlaps with the spray cone (s) of the first nozzle or the first pair of nozzles.
  • the metal deposition bath is sprayed in the form of two partial baths from the second and third nozzle or the second and third pairs of nozzles, these are adjusted so that their spray cones fully meet on the substrate surface.
  • the two partial baths are then alternately sprayed from further nozzles or pairs of nozzles so that the spray cones partially overlap.
  • the concentration of the metal deposition bath on the substrate with the pre-transport is gradually increased until after passing through the last nozzle the bath concentration corresponding to the desired layer thickness has been reached.
  • the substrate surface is then freed from the bath residues and residues in a conventional manner by rinsing with water.
  • the metal deposition bath can be sprayed in a completely mixed form - this is possible, for example, in cases where the metal deposition is only catalyzed by an activator located on the substrate surface - it is advantageous to use a diluted one from the second nozzle and from the third and to spray more and more concentrated baths in the following nozzles.
  • a concentration gradient forms on the substrate in the direction of movement, which leads to a particularly uniform metal coating.
  • the spray pressure and spray angle of the nozzles are preferably set such that the initial concentration of the metal deposition bath on the substrate surface is 50 to 5%, in particular 10 to 30% of the maximum concentration.
  • a system for the production of silver mirrors consists of a 140 cm wide conveyor belt on which cleaned and activated with a tin (II) salt solution in a known manner glass plates are transported at a speed between 100 and 260 cm per minute under a nozzle bar, which in 20 - 40 cm height above the conveyor belt makes 18 back and forth movements per minute across the entire width.
  • nozzle bar 4 pairs of nozzles are arranged one behind the other in an angle-adjustable manner (nozzles 1 - 4), from which the metal deposition bath or the partial baths can be sprayed under a pressure of 3 to 6 bar.
  • a further angle-adjustable nozzle with twice the capacity is attached to the nozzle bar, from which additional water can be sprayed onto the glass plates that are transported past on the conveyor belt.
  • aqueous ammoniacal silver nitrate solutions were used in concentrations of 0.5 to 3.5% and in each case equivalent amounts of a commercially available reducing agent (R) based on a sugar derivative. These solutions are sprayed through the paired nozzles onto the glass plates that are moving past. After every 2 minutes, measured from the impact of the first spray jet on the activated glass, it is rinsed with pure water through subsequent nozzles and dried. The mirrors obtained were assessed by determining the amount of silver deposited per unit area (mean value with spread). In some runs, according to the invention, water was sprayed on beforehand, in others according to the prior art, without this measure. The results are summarized in the following table:
  • the table clearly shows that by additionally spraying water through the nozzle W (runs 5 to 8), the initial bath concentration on the glass plates rose from 3.5% to about 1.5% and from 1.75% to about 0 , 15% is reduced, much more uniform silver levels are obtained than without this measure.
  • This can also be clearly seen when looking at the silver mirrors produced in transmitted light, where the silver layers obtained in runs 1 to 4 clearly show a granular structure which is not recognizable in the runs 5 to 8 produced.
  • the adhesive strength of the silver layers with the granular structure is significantly lower; here the silver layer can be removed by scratching with the fingernail, while this is not possible with the silver layers produced in runs 5 to 8.

Abstract

1. Process for the electroless deposition of a uniform layer of metal by spraying an aqueous metal deposition solution containing a metal salt and a reducing agent, characterized in that, by lowering the solution concentration at the point where the sprayed metal deposition solution first makes contact with the substrate surface to about 50 to 5 % of the concentration in the spray jet, a cohesive thin coating of metal is first produced on the substrate surface, which coating is increased to the desired thickness by subsequent treatment with a deposition solution of the customary concentration.

Description

Die Erfindung betrifft ein Verfahren zur stromlosen Metallabscheidung.The invention relates to a method for electroless metal deposition.

Es ist bekannt, durch Aufsprühen von wässerigen Lösungen von Metallsalzen und geeigneten Reduktionsmitteln auf Substratoberflächen auf diesen Metallschichten abzuscheiden. Auf diese Weise werden heute beispielsweise Überzüge von Gold, Silber, Kupfer, Nickel, Kobalt, Chrom, Platin und Palladium auf den verschiedensten Substratmaterialien erzeugt. Gegenüber der ebenfalls häufigen galvanischen Metallabscheidung haben die stromlosen Verfahren den Vorteil, daß die zu beschichtende Substratoberfläche nicht elektrisch leitfähig sein oder gemacht werden muß. Außerdem ist die Verteilung des abgeschiedenen Metalls auf der gesamten zu beschichtenden Substratoberfläche gewöhnlich gleichmäßiger, weil sie nicht von der Stromdichte abhängig ist, die insbesondere bei nicht völlig ebenen Oberflächen auch an räumlich benachbarten Flächenelementen sehr unterschiedlich sein kann.It is known to deposit metal salts and suitable reducing agents on substrate surfaces by spraying on aqueous solutions of these metal layers. In this way, for example, coatings of gold, silver, copper, nickel, cobalt, chromium, platinum and palladium are produced on a wide variety of substrate materials. Compared to the likewise frequent galvanic metal deposition, the currentless processes have the advantage that the substrate surface to be coated does not have to be electrically conductive or has to be made. In addition, the distribution of the deposited metal is usually more uniform over the entire substrate surface to be coated, because it is not dependent on the current density, which can be very different, particularly in the case of not completely flat surfaces, even on spatially adjacent surface elements.

Indessen ist auch bei der stromlosen Metallabscheidung, die im technischen Maßstab überwiegend durch Aufsprühen der Metallabscheidungsbäder auf die Substratoberfläche erfolgt, die Schichtdicke nicht immer an allen Stellen so gleichmäßig, wie es zur wirtschaftlichen Ausnutzung der in den Bädern enthaltenen Metallsalze erwünscht ist.However, even in the case of electroless metal deposition, which takes place on an industrial scale predominantly by spraying the metal deposition baths onto the substrate surface, the layer thickness is not always as uniform at all points as is desirable for the economic utilization of the metal salts contained in the baths.

Bei den gebräuchlichen Metallabscheidungsbädern werden zwei oder mehrere Teilbäder - eines mit dem Metallsalz, ein zweites mit dem notwendigen Reduktionsmittel, gegebenenfalls weitere mit Zusatzstoffen wie Komplexbildnern, Stabilisatoren und/oder Glanzbildnern - gleichzeitig, aber getrennt versprüht, um eine Metallabscheidung vor dem Auftreffen auf die zu beschichtende Substratoberfläche zu vermeiden. Soweit für dieses Versprühen Luft-Zerstäubungsdüsen eingesetzt werden, wird zwar eine sehr feine Vernebelung der Teilbäder und damit eine gute Durchmischung auf der zu beschichtenden Oberfläche erreicht; gleichzeitig 'werden aber von den bei dieser Arbeitsweise notwendigen Absaugvorrichtungen für die Abluft auch beträchtliche Anteile der feinen Nebeltröpfchen mit abgesaugt, die eine Metallabscheidung in den Absaugkanälen bewirken, wo sie unerwünscht ist und unter bft hohem Kostenaufwand entfernt werden muß. Bei dem aus diesem Grund häufiger angewendeten Versprühen aus Naßzerstäuberdüsen (Airless-Verfahren) werden wesentlich größere Sprühtröpfchen erhalten..Die Metallabscheidung auf der Substratoberfläche beginnt nun überall an den Stellen, wo Sprühtröpfchen des Metallsalz-Teilbades mit solchen des Reduktionsmittel-Teilbades zusammentreffen. Dabei sind die Mischungsverhältnisse an manchen Stellen richtig für eine sofort beginnende festhaftende Metallab- scheidung, an anderen Stellen dazwischen aber werden die für die Abscheidung notwendigen Konzentrationen der Reaktionspartner erst etwas später erreicht. Die dabei nur Sekundenbruchteile voneinander verschiedenen Anfangszeiten der Metallabscheidung bewirken so eine zunächst punktförmige Abscheidung, wobei sich diese Punkte dann solange verstärken und soweit ausdehnen, bis sie zu einer flächenhaften Beschichtung zusammenwachsen. Auf diese Weise entsteht ein zwar makroskopisch gleichmäßiger Metallbelag, der jedoch im Mikrobereich eine körnige Struktur aufweist, in der die Schichtdicken in benachbarten Mikrobereichen sich um ein Mehrfaches voneinander unterscheiden können. Die Qualität jeder Metallbeschichtung ist in der Regel durch die Stellen mit der geringsten Schichtdicke bestimmt; zur Erzielung einer insgesamt befriedigenden Beschichtungsqualität wird daher wesentlich mehr Metallbeschichtungsbad verbraucht. als der notwendigen Mindestschichtdicke entspricht. Besonders bei Edelmetallbeschichtungen, zum Beispiel bei der Herstellung von Spiegeln durch Versilberung von Glas, bedeutet die Menge des Metalls, das an den Stellen mit hoher Schichtdicke überflüssig abgeschieden ist, einen beachtlichen Verlust.In the conventional metal deposition baths, two or more sub-baths - one with the metal salt, a second with the necessary reducing agent, optionally further with additives such as complexing agents, stabilizers and / or brightening agents - are sprayed simultaneously but separately in order to separate the metal before it hits it to avoid coating the substrate surface. To the extent that air atomizing nozzles are used for this spraying, very fine atomization of the partial baths and thus thorough mixing on the surface to be coated are achieved; At the same time, however, a considerable proportion of the fine mist droplets are also sucked off by the suction devices for the exhaust air which are necessary in this way of working and which cause metal separation in the suction channels, where it is undesirable and has to be removed at great expense. For this reason, spraying from wet atomizing nozzles (airless method), which is used more frequently, results in much larger spray droplets. The metal deposition on the substrate surface now begins wherever spray droplets of the metal salt partial bath meet those of the reducing agent partial bath. Here the mixing ratios are distinctive in some places right for an immediate starting adherent M etallab-, intervening in other places but necessary for the deposition reactant concentrations are achieved only a little later. The starting times of the metal deposition, which differ from one another for only a fraction of a second, result in an initially punctiform deposition, these points then strengthening and expanding until they grow together to form a flat coating. In this way, a macroscopically uniform metal coating is created, which, however, has a granular structure in the micro-range in which the layer thicknesses in neighboring micro-ranges can differ from one another by a multiple. The quality of each metal coating is usually determined by the points with the smallest layer thickness; To achieve an overall satisfactory coating quality, considerably more metal coating bath is therefore used. corresponds to the necessary minimum layer thickness. Particularly in the case of precious metal coatings, for example in the production of mirrors by silvering glass, the amount of metal which is unnecessarily deposited at the locations with a high layer thickness means a considerable loss.

Aufgabe der vorliegenden Erfindung war die Bereitstellung eines Verfahrens zur stromlosen Metallabscheidung durch Versprühen eines Metallabscheidungsbades, bei dem das Metall in möglichst gleichmäßiger Schichtdicke abgeschieden wird.The object of the present invention was to provide a method for electroless metal deposition by spraying a metal deposition bath, in which the metal is deposited in a layer thickness that is as uniform as possible.

Es wurde nun gefunden, daß eine sehr gleichmäßige Metallschicht durch Aufsprühen eines wässerigen Metallabscheidungsbades auf eine Substratoberfläche hergestellt werden kann, wenn das Metallabscheidungsbad im Augenblick des Auftreffens auf die Substratoberfläche mit Wasser verdünnt wird. Die Abscheidungsgeschwindigkeit wird wesentlich von den Konzentrationen der Reaktionspartner in den sich vereinigenden aufgesprühten Tröpfchen bestimmt. Wenn die Konzentration durch das Zumischen von Wasser im Augenblick des Auftreffens verringert wird, ist die Zeit bis zum Beginn der Metallabscheidung länger. In dieser Zeit kann eine vollständige Durchmischung der aufgesprühten Tröpfchen erfolgen, so daß die Metallabscheidung nicht punktförmig beginnt, sondern flächenhaft in Form einer sehr dünnen, aber geschlossenen Schicht. Der gleiche Effekt wird erzielt, wenn zunächst stark verdünnte Lösungen des Metallsalz-Teilbades und des Reduktionsmittel-Teilbades durch separate Düsen zur Bildung eines gut durchmischten, stark verdünnten Metallabscheidungsbades aufgesprüht werden.It has now been found that a very uniform metal layer can be produced by spraying an aqueous metal deposition bath onto a substrate surface if the metal deposition bath is diluted with water at the moment it hits the substrate surface. The rate of separation is essentially determined by the concentrations of the reactants in the sprayed droplets that unite. If the concentration is reduced by the addition of water at the moment of impact, the time until the metal deposition begins is longer. During this time, the sprayed-on droplets can be thoroughly mixed so that the metal deposition does not begin in a punctiform manner, but rather in the form of a very thin but closed layer. The same effect is achieved if initially very dilute solutions of the metal salt partial bath and the reducing agent partial bath are sprayed on through separate nozzles to form a well-mixed, highly diluted metal deposition bath.

Gegenstand der Erfindung ist somit das Verfahren zur stromlosen Abscheidung einer gleichmäßigen Metallschicht durch Aufsprühen eines ein Metallsalz und ein Reduktionsmittel und gegebenenfälls weitere Zusatzstoffe enthaltenden Metallabscheidungsbades auf eine Substratoberfläche, das dadurch gekennzeichnet ist, daß durch Herabsetzung der Badkonzentration zunächst ein zusammenhängender dünner Metallüberzug auf der Substratoberfläche erzeugt wird, der durch anschließende Behandlung mit einem Abscheidungsbad üblicher Konzentration bis zur gewünschten Dicke verstärkt wird.The invention thus relates to the process for the electroless deposition of a uniform metal layer by spraying a metal deposition bath containing a metal salt and a reducing agent and possibly further additives onto a substrate surface, which is characterized in that by reducing the bath concentration, a coherent thin metal coating is first produced on the substrate surface is, which is strengthened by subsequent treatment with a deposition bath of conventional concentration to the desired thickness.

Aus der US-PS 3 983 266 ist es zwar bekannt, bei der stromlosen Versilberung von Glas zur Spiegelherstellung vor dem Aufsprühen des Versilberungsbades das Substrat mit Wasser von etwa 50 °C zu besprühen. Bei diesem Verfahren geschieht dieses Besprühen mit warmem Wasser jedoch nur zu dem Zweck, um die Glasplatten vor der Versilberung zu erwärmen und überschüssige Aktivierungslösung abzuspülen. Aus dieser Patentschrift ist nicht zu entnehmen, daß das Wasser zum Zweck der anfänglichen Verdünnung der anschließend aufgesprühten Versilberungslösung aufgesprüht wird, und erst recht nicht der überraschende Effekt, daß dadurch besonders gleichmäßige silberschichten erzielt werden.From US Pat. No. 3,983,266, it is known in the case of electroless silvering of glass for mirror production before the silvering bath is sprayed on the substrate spray with water at around 50 ° C. In this method, however, this spraying with warm water is only for the purpose of heating the glass plates before silvering and rinsing off excess activation solution. It is not apparent from this patent that the water is sprayed on for the purpose of initially diluting the silvering solution subsequently sprayed on, and certainly not the surprising effect that particularly uniform silver layers are achieved as a result.

Das erfindungsgemäße Verfahren ist prinzipiell bei allen üblicherweise stromlos abgeschiedenen Metallbeschichtungen anwendbar. Da es deutliche Einsparungen an Metallsalzen ermöglicht, wird es bevorzugt bei der Aufbringung von Edelmetallschichten, zum Beispiel aus Gold, Silber, Platin oder Palladium angewendet. Für jedes nach dem erfindungsgemäßen Verfahren abzuscheidende Metall können die jeweils üblichen Reduktionsmittel verwendet werden, beispielsweise Hypophosphit für Gold, Formaldehyd, Zucker oder Zuckerderivate für Silber, Hydrazinhydrat für Platin oder Palladium.The method according to the invention can in principle be used with all metal coatings which are usually deposited without current. Since it enables significant savings on metal salts, it is preferred for the application of precious metal layers, for example made of gold, silver, platinum or palladium. The customary reducing agents can be used for each metal to be deposited by the process according to the invention, for example hypophosphite for gold, formaldehyde, sugar or sugar derivatives for silver, hydrazine hydrate for platinum or palladium.

Nach dem erfindungsgemäßen Verfahren kann überall da gearbeitet werden, wo ein an sich übliches wässeriges Metallabscheidungsbad auf eine Substratoberfläche aufgesprüht wird. Der erfindungsgemäße Verdünnungsschritt kann dabei auf verschiedene Art und Weise erfolgen. So kann zum Beispiel das Metallabscheidungsbad in eine sich gegebenenfalls bewegende dünne Wasserschicht auf der Substratoberfläche gesprüht werden, wobei die Wassermenge so gewählt wird, daß im Augenblick des Auftreffens des Sprühstrahls auf die Wasserschicht die Konzentration des Bades oder mindestens des Metallsalz-Teilbades auf 50 bis 5 % der Konzentration im Sprühstrahl herabgesetzt wird.The process according to the invention can be used wherever a conventional aqueous metal deposition bath is sprayed onto a substrate surface. The dilution step according to the invention can be carried out in various ways. For example, the metal deposition bath can be sprayed into a possibly moving thin water layer on the substrate surface, the amount of water being selected such that the concentration of the bath or at least the metal salt sub-bath is 50 to 5 at the moment the spray jet hits the water layer % of the concentration in the spray jet is reduced.

In einer bevorzugten Ausführungsform wird das erfindungsgemäße Verfahren bei den praxisüblichen Metallabscheidungsanlagen angewendet, wo das Substrat auf einem Förderband unter einer Anzahl von in der Bewegungsrichtung des Förderbandes hintereinander an einem Balken angeordneten Sprühdüsen entlang bewegt wird, wobei sich der Balken mit den Sprühdüsen quer zur Bewegungsrichtung des Förderbandes über dem Substrat hin und her bewegt. Bei einer derartigen Anlage wird erfindungsgemäß aus der ersten Düse - in Bewegungsrichtung des Förderbandes gesehen - reines Wasser unter einem solchen Druck versprüht, daß sich beim Auftreffen auf das Substrat eine Wasserwelle ausbildet, die abhängig von der Transportgeschwindigkeit des Bandes und dem Aufsprühmittel mit ihrer größten Amplitude in einer geringen Entfernung vor dem Sprühkegel entlangläuft. Die zweite und gegebenenfalls weitere Düsen bzw. Düsenpaare,aus denen das Metallisierungsbad, gegebenenfalls auch in Form von Teilbädern, versprüht wird, werden dann so eingestellt, daß sich deren Sprühkegel partiell mit. dem der Wasserdüse überlappt, wobei das Zentrum des Sprühkegels der zweiten Düse bzw. Düsenpaares etwa über die höchste Stelle der vor dem ersten Sprühkegel entlanglaufenden Wasserwelle eingestellt wird. Es kann jedoch auch zweckmäßig sein, den Sprühkegel der Wasser-Düse(n) so einzustellen, daß er sich vollständig mit dem (den) Sprühkegel(n) der ersten Düse bzw. des ersten Düsenpaares überlappt. Wenn aus der zweiten und dritten Düse bzw. den zweiten und dritten Düsenpaaren das Metallabscheidungsbad in Form von zwei Teilbädern versprüht wird, werden diese so eingestellt, daß ihre Sprühkegel auf der Substratoberfläche voll zusammentreffen. Aus weiteren Düsen bzw. Düsenpaaren werden dann immer abwechselnd die beiden Teilbäder so.versprüht, daß sich die Sprühkegel partiell überlappen. Auf diese Weise wird die Konzentration des Metallabscheidungsbades auf dem Substrat mit dem Vortransport stufenweise erhöht, bis nach dem Passieren der letzten Düse die der gewünschten Schichtdicke entsprechende Badkonzentration erreicht ist. Nach einer für das jeweilige Metallabscheidungsbad spezifischen Reaktionszeit wird dann die Substratoberfläche in an sich üblicher Weise durch Abspülen mit Wasser von den Badresten und -rückständen befreit.In a preferred embodiment, the method according to the invention is applied to the metal deposition systems customary in practice, where the substrate is moved on a conveyor belt under a number of spray nozzles arranged one behind the other in the direction of movement of the conveyor belt, the beam with the spray nozzles moving transversely to the direction of movement of the Conveyor belt moved back and forth over the substrate. In such a system, according to the invention, pure water is sprayed from the first nozzle - as seen in the direction of movement of the conveyor belt - under such a pressure that a water wave forms when it hits the substrate, which, depending on the transport speed of the belt and the spraying agent, has its greatest amplitude runs a short distance in front of the spray cone. The second and possibly further nozzles or pairs of nozzles, from which the metallization bath, optionally also in the form of partial baths, is sprayed, are then set such that their spray cones are partially coexistent. that of the water nozzle overlaps, the center of the spray cone of the second nozzle or pair of nozzles being set approximately above the highest point of the water wave running in front of the first spray cone. However, it may also be expedient to set the spray cone of the water nozzle (s) so that it completely overlaps with the spray cone (s) of the first nozzle or the first pair of nozzles. If the metal deposition bath is sprayed in the form of two partial baths from the second and third nozzle or the second and third pairs of nozzles, these are adjusted so that their spray cones fully meet on the substrate surface. The two partial baths are then alternately sprayed from further nozzles or pairs of nozzles so that the spray cones partially overlap. In this way, the concentration of the metal deposition bath on the substrate with the pre-transport is gradually increased until after passing through the last nozzle the bath concentration corresponding to the desired layer thickness has been reached. After a reaction time that is specific to the respective metal deposition bath, the substrate surface is then freed from the bath residues and residues in a conventional manner by rinsing with water.

wenn das Metallabscheidungsbad in fertig gemischter Form versprüht werden kann - dies ist zum Beispiel in den Fällen möglich, wo die Metallabscheidung erst durch einen auf der Substratoberfläche befindlichen Aktivator katalysiert wird -, ist es vorteilhaft, aus der zweiten Düse ein verdünntes und aus der dritten und den folgenden Düsen immer konzentriertere Bäder zu versprühen. In diesem Fall bildet sich auf dem Substrat in Bewegungsrichtung ein Konzentrationsgefälle aus, das zu einer besonders gleichmäßigen Metallbeschichtung führt. Auch in dieser Ausführungsform des erfindungsgemäßen Verfahrens werden Sprühdruck und Sprühwinkel der Düsen vorzugsweise so eingestellt, daß die Anfangskonzentration des Metallabscheidungsbades auf der Substratoberfläche 50 bis 5 %, insbesondere 10 bis 30 % der Maximalkonzentration beträgt.if the metal deposition bath can be sprayed in a completely mixed form - this is possible, for example, in cases where the metal deposition is only catalyzed by an activator located on the substrate surface - it is advantageous to use a diluted one from the second nozzle and from the third and to spray more and more concentrated baths in the following nozzles. In this case, a concentration gradient forms on the substrate in the direction of movement, which leads to a particularly uniform metal coating. In this embodiment of the method according to the invention, the spray pressure and spray angle of the nozzles are preferably set such that the initial concentration of the metal deposition bath on the substrate surface is 50 to 5%, in particular 10 to 30% of the maximum concentration.

Beispielexample a) Anlagea) Appendix

Eine Anlage zur Herstellung von Silberspiegeln . besteht aus einem 140 cm breiten Förderband, auf dem gereinigte und mit einer Zinn-(II)-salz-Lösung in an sich bekannter Weise aktivierte Glasplatten mit einer Geschwindigkeit zwischen 100 und 260 cm pro Minute unter einem Düsenbalken entlangtransportiert werden, der in 20 - 40 cm Höhe über dem Förderband 18 Hin- und Herbewegungen in der Minute über die gesamte Breite macht. An dem Düsenbalken sind hintereinander 4 Düsenpaare winkelverstellbar angeordnet (Düsen 1 - 4), aus denen das Metallabscheidungsbad bzw. die Teilbäder unter einem Druck von 3 bis 6 bar versprüht werden kann. Im Abstand von 5 cm vor dem ersten Düsenpaar ist an dem Düsenbalken eine weitere winkelverstellbare Düse mit der doppelten Leistungsfähigkeit angebracht (Düse W), aus der zusätzlich Wasser auf die auf dem Förderband vorbeitransportierten Glasplatten gesprüht werden kann.A system for the production of silver mirrors. consists of a 140 cm wide conveyor belt on which cleaned and activated with a tin (II) salt solution in a known manner glass plates are transported at a speed between 100 and 260 cm per minute under a nozzle bar, which in 20 - 40 cm height above the conveyor belt makes 18 back and forth movements per minute across the entire width. On the nozzle bar 4 pairs of nozzles are arranged one behind the other in an angle-adjustable manner (nozzles 1 - 4), from which the metal deposition bath or the partial baths can be sprayed under a pressure of 3 to 6 bar. At a distance of 5 cm in front of the first pair of nozzles, a further angle-adjustable nozzle with twice the capacity (nozzle W) is attached to the nozzle bar, from which additional water can be sprayed onto the glass plates that are transported past on the conveyor belt.

b) Materialien und Arbeitsweiseb) Materials and working methods

Für die Verspiegelung wurden wässerig-ammoniakalische Silbernitratlösungen(S) in Konzentrationen von 0,5 bis 3,5 % und jeweils äquivalente Mengen eines handelsüblichen Reduktionsmittels (R) auf der Basis eines Zuckerderivats eingesetzt. Diese -Lösungen werden durch die paarweise angeordneten Düsen auf die vorbeibewegten Glasplatten gesprüht. Nach jeweils 2 Minuten, gemessen vom Auftreffen- des ersten Sprühstrahls auf das aktivierte Glas, wird dieses durch nachgeschaltete weitere Düsen mit reinem Wasser abgespült und getrocknet. Die erhaltenen Spiegel wurden durch Bestimmung der abgeschiedenen Silbermenge pro Flächeneinheit (Mittelwert mit Streubreite) beurteilt. Dabei wurde in einigen Läufen erfindungsgemäß mit vorherigem Aufsprühen von Wasser, in anderen nach dem Stand der Technik ohne diese Maßnahme gearbeitet. Die Ergebnisse sind in der folgenden Tabelle zusammengestellt:

Figure imgb0001
For the mirroring, aqueous ammoniacal silver nitrate solutions (S) were used in concentrations of 0.5 to 3.5% and in each case equivalent amounts of a commercially available reducing agent (R) based on a sugar derivative. These solutions are sprayed through the paired nozzles onto the glass plates that are moving past. After every 2 minutes, measured from the impact of the first spray jet on the activated glass, it is rinsed with pure water through subsequent nozzles and dried. The mirrors obtained were assessed by determining the amount of silver deposited per unit area (mean value with spread). In some runs, according to the invention, water was sprayed on beforehand, in others according to the prior art, without this measure. The results are summarized in the following table:
Figure imgb0001

Die Tabelle zeigt deutlich, daß durch das zusätzliche Aufsprühen von Wasser durch die Düse W (Läufe 5 bis 8) wodurch die anfängliche Badkonzentration auf den Glasplatten von 3,5 % auf etwa 1,5 % bzw. vn 1,75 % auf etwa 0,15 % herabgesetzt wird, wesentlich gleichmäßigere Silberspiegel erhalten werden als ohne diese Maßnahme. Dies ist auch bei der Betrachtung der hergestellten Silberspiegel im Durchlicht deutlich zu erkennen, wo die bei den Läufen 1 bis 4 erhaltenen Silberschichten deutlich eine körnige Struktur erkennen lassen, die bei den in den Läufen 5 bis 8 hergestellten nicht erkennbar ist. Darüberhinaus ist die Haftfestigkeit der Silberschichten mit der körnigen Struktur wesentlich geringer; hier läßt sich die Silberschicht durch Kratzen mit dem Fingernagel entfernen, während dies bei den in den Läufen 5 bis 8 hergestellten Silberschichten nicht möglich ist.The table clearly shows that by additionally spraying water through the nozzle W (runs 5 to 8), the initial bath concentration on the glass plates rose from 3.5% to about 1.5% and from 1.75% to about 0 , 15% is reduced, much more uniform silver levels are obtained than without this measure. This can also be clearly seen when looking at the silver mirrors produced in transmitted light, where the silver layers obtained in runs 1 to 4 clearly show a granular structure which is not recognizable in the runs 5 to 8 produced. In addition, the adhesive strength of the silver layers with the granular structure is significantly lower; here the silver layer can be removed by scratching with the fingernail, while this is not possible with the silver layers produced in runs 5 to 8.

Claims (5)

1. Verfahren zur stromlosen Abscheidung einer gleichmäßigen Metallschicht durch Aufsprühen eines ein Metallsalz und ein Reduktionsmittel enthaltenden wäßrigen Metallabscheidungsbades,.dadurch gekennzeichnet, daß durch Herabsetzung der Badkonzentration zunächst ein zusammenhängender dünner Metallüberzug auf der Substratoberfläche erzeugt wird, der durch anschließende Behandlung mit einem Abscheidungsbad üblicher Konzentration bis zur gewünschten Dicke verstärkt wird.1. A method for the electroless deposition of a uniform metal layer by spraying on an aqueous metal deposition bath containing a metal salt and a reducing agent, characterized in that by reducing the bath concentration a coherent thin metal coating is first produced on the substrate surface, which is subsequently treated with a deposition bath of the usual concentration is strengthened to the desired thickness. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß zu Beginn der Abscheidung beim ersten Auftreffen des versprühten Metallabscheidungsbades auf die Substratoberfläche die Konzentration mindestens des das Metallsalz enthaltenden Teilbades auf etwa 50 bis 5 % des für die nachfolgende Abscheidung verwendeten Metallsalz-Teilbades vermindert wird.2. The method according to claim 1, characterized in that at the beginning of the deposition when the sprayed metal deposition bath first hits the substrate surface, the concentration of at least the sub-bath containing the metal salt is reduced to about 50 to 5% of the sub-bath used for the subsequent deposition. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Konzentration des Metallabscheidungsbades am Ort des ersten Auftreffens auf etwa 50 bis 5 % der Konzentration im Sprühstrahl des Metallsalz-Teilbades vermindert wird.3. The method according to claim 1, characterized in that the concentration of the metal deposition bath at the location of the first impact is reduced to about 50 to 5% of the concentration in the spray of the metal salt sub-bath. 4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Verdünnung dadurch vorgenommen wird, daß durch eine der ersten Metallabscheidungsbad- oder -teilbad-Düse vorgeschaltete Düse vorab Wasser auf die Substratoberfläche gesprüht wird.4. The method according to claims 1 to 3, characterized in that the dilution is carried out in that water is sprayed in advance through a nozzle upstream of the first metal deposition bath or partial bath nozzle onto the substrate surface. 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß sich die Sprühkegel der Wasser- und der ersten Metallabscheidungsbad- bzw. -teilbad-Düsen überlappen.5. The method according to claim 4, characterized in that the spray cones of the water and the first metal deposition bath or partial bath nozzles overlap.
EP81101169A 1980-03-28 1981-02-19 Process for the electroless deposition of metals Expired EP0036940B1 (en)

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EP0162979A1 (en) * 1984-05-21 1985-12-04 Carolina Solvents, Inc. Electrically conductive microballoons and compositions incorporating same
US4624798A (en) * 1984-05-21 1986-11-25 Carolina Solvents, Inc. Electrically conductive magnetic microballoons and compositions incorporating same
US5786785A (en) * 1984-05-21 1998-07-28 Spectro Dynamics Systems, L.P. Electromagnetic radiation absorptive coating composition containing metal coated microspheres
WO1998054378A1 (en) * 1997-05-29 1998-12-03 Guy Stremsdoerfer Non-electro-plating method for metallizing a substrate by reduction process of metallic salt(s) and aerosol splattering
EP1067590A2 (en) * 1999-07-09 2001-01-10 Applied Materials, Inc. Electroplating system
US7674401B2 (en) 2001-12-18 2010-03-09 Asahi Kasei Kabushiki Kaisha Method of producing a thin conductive metal film

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DE1771342A1 (en) * 1967-05-12 1971-11-25 Comp Generale Electricite Process for depositing silver on nickel
DE2040930A1 (en) * 1969-08-20 1971-03-04 Crown City Plating Co Electroless metal deposition method
DE2427077A1 (en) * 1973-06-09 1975-01-02 Faq Vos Ltd METHOD OF PLATING METAL SURFACES

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0162979A1 (en) * 1984-05-21 1985-12-04 Carolina Solvents, Inc. Electrically conductive microballoons and compositions incorporating same
US4624798A (en) * 1984-05-21 1986-11-25 Carolina Solvents, Inc. Electrically conductive magnetic microballoons and compositions incorporating same
US4624865A (en) * 1984-05-21 1986-11-25 Carolina Solvents, Inc. Electrically conductive microballoons and compositions incorporating same
US5786785A (en) * 1984-05-21 1998-07-28 Spectro Dynamics Systems, L.P. Electromagnetic radiation absorptive coating composition containing metal coated microspheres
WO1998054378A1 (en) * 1997-05-29 1998-12-03 Guy Stremsdoerfer Non-electro-plating method for metallizing a substrate by reduction process of metallic salt(s) and aerosol splattering
FR2763962A1 (en) * 1997-05-29 1998-12-04 Guy Stremsdoerfer NON-ELECTROLYTIC PROCESS FOR METALLIZING A SUBSTRATE BY MEANS OF REDUCTION OF METAL SALT (S) AND BY SPRAYING AEROSOL (S)
EP1067590A2 (en) * 1999-07-09 2001-01-10 Applied Materials, Inc. Electroplating system
EP1067590A3 (en) * 1999-07-09 2004-05-12 Applied Materials, Inc. Electroplating system
US7674401B2 (en) 2001-12-18 2010-03-09 Asahi Kasei Kabushiki Kaisha Method of producing a thin conductive metal film
DE10297544B4 (en) * 2001-12-18 2015-10-29 Asahi Kasei Kabushiki Kaisha Process for producing a metal thin film

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