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WO1986000649A1 - Method for improving the colour effect of titanium nitride layers - Google Patents

Method for improving the colour effect of titanium nitride layers Download PDF

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Publication number
WO1986000649A1
WO1986000649A1 PCT/EP1985/000324 EP8500324W WO8600649A1 WO 1986000649 A1 WO1986000649 A1 WO 1986000649A1 EP 8500324 W EP8500324 W EP 8500324W WO 8600649 A1 WO8600649 A1 WO 8600649A1
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Prior art keywords
coating
titanium nitride
nitride layers
improving
hydrocarbon
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PCT/EP1985/000324
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German (de)
French (fr)
Inventor
Helmut Steininger
Heinz-Werner Etzkorn
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Battelle Institut eV
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Battelle Institut eV
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases

Definitions

  • the invention relates to a method for improving the color impression of titanium nitride layers by means of plasma-supported coating methods, in particular by means of
  • Magnetron nuts using a process gas consisting of an inert gas and nitrogen.
  • Decorative hard material coatings made of titanium nitride on substrates made of any material such as plastic, ceramic, metal or metal alloy can be deposited using physical coating methods such as magnetron sputtering or ion plating.
  • the color scale of such layers ranges from white to yellow to rose gold. Compared to pure gold layers, however, gold-colored titanium nitride layers are generally perceived as cold. This fact is very disruptive when using titanium nitride for decorative applications, especially as a gold substitute.
  • the color impression of the titanium nitride layers can be influenced by varying the process conditions such as bias voltage and temperature.
  • the morphology of the layer is also changed.
  • the temperature is higher, so the layers show an undesirably stalky appearance.
  • Titanium nitride layers are desired that have the outstanding physical and chemical properties of titanium nitride such as great hardness and thus high scratch resistance and corrosion resistance and also show a warm gold color.
  • the subjective impression of a warm gold color is created e.g. B. by increasing the red value or by reducing the proportion of green, ie the black haze of the layer. This is not achieved by simply increasing the nitrogen content in the titanium nitride layer, since the associated increase in the red value always goes hand in hand with a decrease in the yellow content. Therefore, reddish-brown layers are increasingly obtained.
  • the object of the invention is to increase the red value of titanium nitride layers by a simple variation of the coating conditions, or to reduce the proportion of green without influencing the yellow value of the layer. Furthermore, the process should not cause any change in the physical and chemical properties, in particular the corrosion resistance and the scratch resistance of the titanium nitride.
  • This object is achieved in that carbon is introduced into the reaction space between a target and a substrate to be coated and. that the coating is carried out at substrate temperatures of less than 250 ° C, and that the properties of the layer depend on the substrate temperature and
  • Bias voltage and the color impression can be adjusted via the carbon content. Preferred embodiments of the method according to the invention are described in subclaims 2 to 11.
  • the titanium nitride layers are deposited in a manner known per se by plasma-assisted deposition methods in a vacuum coating apparatus, preferably by magnetron sputtering.
  • a hydrocarbon is admitted to the process gases argon and nitrogen which are usually used. All saturated and unsaturated substituted or unsubstituted hydrocarbons with 1 to 6, preferably 1 to 3, carbon atoms are suitable.
  • the reaction conditions, in particular the bias voltage and the temperature of the substrate, are set to values favorable for advantageous properties of use of the layer, such as adhesion, homogeneity and unity.
  • the red value of the deposited titanium nitride layers depends sensitively on the flow rate of the hydrocarbon introduced into the apparatus.
  • low substrate temperatures of less than 250 ° C, preferably 20 to 200 ° C, are used.
  • the flow rates of the hydrocarbons added to influence the color impression are between about 0.05 and 1 cm 3 / min.
  • carbon is supplied by using a titanium carbide target instead of a pure titanium target.
  • a titanium carbide target instead of a pure titanium target.
  • noble gases preferably argon
  • nitrogen are used as process gases.
  • the flow rate of the nitrogen can also be continuously reduced or increased from about the middle of the total coating time or towards the end of the coating, as a result of which the layer only has the desired color on the surface.
  • the coating is typically carried out at a residual gas pressure of less than 2.10 -6 torr.
  • Deposition rates are between 1 0 and 20 ⁇ / sec. , preferably 1 5 ⁇ / sec.
  • the argon flow rate is e.g. B. 1 0, 5 to 1 3, 5 cm 3 / min. who have favourited Sticks toff flow rate e.g. B. 2 to 1 0 cm 3 / min.
  • the flow rate of the hydrocarbon can be between 0.05 and 1 cm 3 / min. vary.
  • a gold-colored titanium nitride layer is obtained by reactive magnetron sputtering of a pure titanium target on a stainless steel workpiece.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

In order to improve the colour effect of titanium nitride layers prepared according to plasma coating methods with the use of a process gas comprised of rare gas and nitrogen, carbon is introduced in the reaction chamber between a target and a substrate to be coated. Alternatively, hydrocarbons are directed to this effect into the reaction chamber. In another embodiment, a target of titanium carbide is used.

Description

Verfahren zur Verbesserung des Farbeindrucks von Titannitridschichten Process for improving the color impression of titanium nitride layers

Beschreibung:Description:

Die Erfindung betrifft ein Verfahren zur Verbesserung des Farbeindrucks von Titannitrid-Schichten mittels plasmagestützter Beschichtungsmethoden, insbesondere mittelsThe invention relates to a method for improving the color impression of titanium nitride layers by means of plasma-supported coating methods, in particular by means of

MagnetronsDuttern, unter Verwendung eines Prozeßgases aus einem Edelgas und Stickstoff.Magnetron nuts, using a process gas consisting of an inert gas and nitrogen.

Dekorative Hartstoffbeschichtungen aus Titannitrid auf Substraten aus beliebigen Materialien wie Kunststoff, Keramik, Metall oder Metallegierung, können durch physikalische Beschichtungsmethoden wie Magnetronsputtern oder Ionenplattieren abgeschieden werden. Die Farbskala solcher Schichten reicht von Weiß- über Gelb- bis Rotgold. Gegenüber reinen Goldschichten werden goldfarbene Titannitrid-Schichten jedoch im allgemeinen ais kalt empfunden. Dieser Umstand wirkt sich beim Einsatz von Titannitrid für dekorative Anwendungen, insbesondere als Goldersatz, sehr störend aus.Decorative hard material coatings made of titanium nitride on substrates made of any material such as plastic, ceramic, metal or metal alloy can be deposited using physical coating methods such as magnetron sputtering or ion plating. The color scale of such layers ranges from white to yellow to rose gold. Compared to pure gold layers, however, gold-colored titanium nitride layers are generally perceived as cold. This fact is very disruptive when using titanium nitride for decorative applications, especially as a gold substitute.

Es ist bekannt, daß durch Variation der Verfahrensbedingungen wie Biasspannung und Temperatur, der Farbeindruck der Titannitrid-Schichten beeinflußt werden kann. Dabei wird jedoch auch die Morphologie der Schicht geändert. Bei niedriger Biasspannung und/oder niedrigen Temperaturen erhält man z. B. poröse Schichten, ist die Temperatur höher, so zeigen die Schichten ein unerwünscht stengeliges Aussehen.It is known that the color impression of the titanium nitride layers can be influenced by varying the process conditions such as bias voltage and temperature. However, the morphology of the layer is also changed. At low bias voltage and / or low temperatures you get e.g. B. porous layers, the temperature is higher, so the layers show an undesirably stalky appearance.

Gewünscht werden Titannitrid-Schichten, die die herausragenden physikalischen und chemischen Eigenschaften von Titannitrid wie große Härte und damit hohe Kratzfestigkeit und Korrosionsbeständigkeit aufweisen und zudem einen warmen Goldfarbton zeigen. Der subjektive Eindruck eines warmen Goldfarbtons entsteht z. B. durch Erhöhung des Rotwertes beziehungsweise durch eine Verringerung des Grünanteils, d. h. des Schwarzschleiers der Schicht. Dies wird durch bloße Erhöhung des Stickstoffgehalts in der Titannitrid-Schicht nicht erreicht, da die damit verbundene Erhöhung des Rotwertes stets mit einer Abnahme des Gelbanteils einhergeh.t. Daher werden zunehmend rötlich-braune Schichten erhalten.Titanium nitride layers are desired that have the outstanding physical and chemical properties of titanium nitride such as great hardness and thus high scratch resistance and corrosion resistance and also show a warm gold color. The subjective impression of a warm gold color is created e.g. B. by increasing the red value or by reducing the proportion of green, ie the black haze of the layer. This is not achieved by simply increasing the nitrogen content in the titanium nitride layer, since the associated increase in the red value always goes hand in hand with a decrease in the yellow content. Therefore, reddish-brown layers are increasingly obtained.

Der Erfindung liegt die Aufgabe zugrunde, den Rotwert von Titannitrid-Schichten durch eine einfache durchzuführende Variation der Beschichtungsbedingungen zu erhöhen, beziehungsweise den Grünanteil zu senken, ohne den Gelbwert der Schicht zu beeinflussen. Ferner sollte das Verfahren keine Änderung der physikalischen und chemischen Eigenschaften, insbesondere der Korrosionsbeständigkeit und der Kratzfestigkeit des Titannitrids, bewirken.The object of the invention is to increase the red value of titanium nitride layers by a simple variation of the coating conditions, or to reduce the proportion of green without influencing the yellow value of the layer. Furthermore, the process should not cause any change in the physical and chemical properties, in particular the corrosion resistance and the scratch resistance of the titanium nitride.

Diese Aufgabe ist erfindungsgemäß dadurch gelöst, daß in den Reaktionsraum zwischen einem Target und einem zu beschichtenden Substrat Kohlenstoff eingebracht wird und. daß die Beschichtung bei Substrattemperatu ren von weniger als 250 ºC durchgeführt wird, und daß die Gebrauchseigenschaften der Schicht über die Substrattemperatur undThis object is achieved in that carbon is introduced into the reaction space between a target and a substrate to be coated and. that the coating is carried out at substrate temperatures of less than 250 ° C, and that the properties of the layer depend on the substrate temperature and

Biasspannung und der Farbeindruck über den Kohlenstoffanteil eingestellt werden. Bevorzugte Ausführungsformen des erfindungsgemäßen Verfahrens sind in den ünteransprüchen 2 bis 11 beschrieben.Bias voltage and the color impression can be adjusted via the carbon content. Preferred embodiments of the method according to the invention are described in subclaims 2 to 11.

Die Abscheidung der Titannitrid-Schichten erfolgt auf an sich bekannte Weise durch plasmagestützte Abscheidemethoden in einer Vakuumbeschichtungsapparatur, vorzugsweise durch Magnetronsputtern. In einer Variante des erfin dungsgemäßen Verfahrens wird zu den üblicherweise verwendeten Prozeßgasen Argon und Stickstoff ein Kohlenwasserstoff eingelassen. Geeignet sind alle gesättigten und ungesättigten substituierten oder unsubstituierten KohlenWasserstoffe mit 1 bis 6, vorzugsweise 1 bis 3 Kohlenstoff-Atomen. Die Reaktionsbedingungen, insbesondere die Biasspannung und die Temperatur des Substrats werden auf für vorteilhafte Gebrauchseigenschaften der Schicht, wie Haftung, Homo genität und Geschlossenheit, günstige Werte eingestellt. Überraschenderweise zeigt es sich, daß bei vorgegebenen Abscheidearten und konstant gehaltenem Argon- und Stickstoffdurchfluß der Rotwert der abgeschiedenen Titannitrid-Schichten empfindlich von der Durchflußmenge des in die Apparatur eingeleiteten KohlenWasserstoffs abhängt. Erfindungsgemäß werden, verglichen mit bekannten Verfahren, niedrige Substrattemperaturen von weniger als 250 ºC, vorzugsweise 20 bis 200 °C, verwendet. Die Durchflußmengen der zur Beeinflussung des Farbeindrucks zugesetzten Kohlenwasserstoffe liegen zwischen etwa 0,05 und 1 cm3/Min. Nach dem erfindungsgemäßen Verfahren ist es auch möglich, den Kohlenwasserstoff erst etwa ab der Mitte der gesamten Beschichtungszeit oder gar erst gegen Ende der Beschichtung dem Reaktionsraum zuzuführen und dabei die Durchflußmenge kontinuierlich von null bis auf etwa 1 cm3/Min. zu steigern. Dadurch wird der Farbeindruck lediglich in dem äußeren Teil der Schicht verbessert.The titanium nitride layers are deposited in a manner known per se by plasma-assisted deposition methods in a vacuum coating apparatus, preferably by magnetron sputtering. In a variant of the invent In accordance with the method according to the invention, a hydrocarbon is admitted to the process gases argon and nitrogen which are usually used. All saturated and unsaturated substituted or unsubstituted hydrocarbons with 1 to 6, preferably 1 to 3, carbon atoms are suitable. The reaction conditions, in particular the bias voltage and the temperature of the substrate, are set to values favorable for advantageous properties of use of the layer, such as adhesion, homogeneity and unity. Surprisingly, it turns out that, with given types of separation and constant argon and nitrogen flow, the red value of the deposited titanium nitride layers depends sensitively on the flow rate of the hydrocarbon introduced into the apparatus. According to the invention, compared to known methods, low substrate temperatures of less than 250 ° C, preferably 20 to 200 ° C, are used. The flow rates of the hydrocarbons added to influence the color impression are between about 0.05 and 1 cm 3 / min. According to the method according to the invention, it is also possible to supply the hydrocarbon to the reaction space only from about the middle of the total coating time or even towards the end of the coating, and the flow rate continuously from zero to about 1 cm 3 / min. to increase. As a result, the color impression is only improved in the outer part of the layer.

Nach einer weiteren Ausführungsform des erfindunsgemäßen Verfahrens wird Kohlenstoff durch Verwendung eines Titancarbid-Targets anstelle eines reinen Titan-Targets zugeführt. In diesem Fall werden als Prozeßgase nur Edelgase, vorzugsweise Argon, und Stickstoff eingesetzt. Bei vorgegebenen Abscheideparametern wie Abscheiderate, Edelgas durchfluß und Biasspannung usw. hängt der Farbton der abgeschiedenen Titannitrid-Schicht allein von dem eingestellten Stickstoff-Durchfluß ab. Die Durchflußmenge des Stickstoffs kann auch hier ab etwa der Mitte der gesamten Beschichtungszeit oder gegen Ende der Beschichtung kontinuierlich reduziert oder erhöht werden, wodurch die Schicht erst an der Oberfläche den erwünschten Farbton aufweist.According to a further embodiment of the method according to the invention, carbon is supplied by using a titanium carbide target instead of a pure titanium target. In this case, only noble gases, preferably argon, and nitrogen are used as process gases. With specified separation parameters such as separation rate, inert gas flow and bias voltage, etc., the color of the deposited titanium nitride layer depends solely on the set nitrogen flow. The flow rate of the nitrogen can also be continuously reduced or increased from about the middle of the total coating time or towards the end of the coating, as a result of which the layer only has the desired color on the surface.

Die Beschichtung wird typischerweise bei einem Restgasdruck von weniger als 2,10-6 Torr durchgeführt. DieThe coating is typically carried out at a residual gas pressure of less than 2.10 -6 torr. The

Abscheideraten liegen zwischen 1 0 und 20 Å/Sek. , vorzugsweise 1 5 Å/Sek . Die Argon-Durchf lußrate beträgt z. B. 1 0 , 5 b is 1 3 , 5 cm3/Min. , die Sticks toff-Durchflußrate z . B. 2 b is 1 0 cm3/Min. Die Durchf lußmenge des KohlenWasserstoffs kann zwischen 0 , 05 und 1 cm3/Min. variieren.Deposition rates are between 1 0 and 20 Å / sec. , preferably 1 5 Å / sec. The argon flow rate is e.g. B. 1 0, 5 to 1 3, 5 cm 3 / min. who have favourited Sticks toff flow rate e.g. B. 2 to 1 0 cm 3 / min. The flow rate of the hydrocarbon can be between 0.05 and 1 cm 3 / min. vary.

Die Erfindung wird anhand des nachfolgenden Beispiels näher erläutert:The invention is illustrated by the following example:

Beispiel:Example:

Bei einer Abscheiderate- von 15 Å/Sek. und einem Argonund Stickstoffdurchfluß von 13,5 cm3/Min. bzw. 3,06 cm3/ Min. wird durch reaktives Magnetronsputtern eines reinen Titan-Targets auf einem Edelstahl-Werkstück eine goldfarbene Titannitrid-Schicht erhalten. Die an dieser Schicht unter Verwendung einer D65 Lichtguelle gemessenen Farbkoordinaten (CIE 1976) L* (Brillanz), a* (Rotwert) und b* (Gelbwert) betragen L* = 59,9, a* = 3,0 und b* = 30,3. Läßt man unter sonst gleichen Bedingungen zusätzlich einen Kohlenwasserstoff z. B. Acetylen mit Durchflußraten von beispielsweise 0,25 und 0,50 cm3/Min. ein, so erhält man für die abgeschiedenen Titannitrid- Schichten Farbkoordinaten von L* = 55,7, a* = 5,8 und b* = 30,3 bzw. L* = 55,0, a* = 7,5 und b* = 25,4. Die Zunahme des Rotwertes a* bei Kohlenstoffzugäbe während der Titannitrid-Abscheidung ohne Änderung des Gelbwertes b* ist im ersteren Fall signifikant. Das Beispiel macht aber auch deutlich, daß bei ansonsten vorgegebenen Prozeßbedingungen ein Maximum der Kohlenwasserstoff-Zugabe existiert, oberhalb dessen der Gelbwert abzunehmen beginnt. At a deposition rate of 15 Å / sec. and an argon and nitrogen flow of 13.5 cm 3 / min. or 3.06 cm 3 / min., a gold-colored titanium nitride layer is obtained by reactive magnetron sputtering of a pure titanium target on a stainless steel workpiece. The color coordinates measured on this layer using a D65 light source (CIE 1976) L * (brilliance), a * (red value) and b * (yellow value) are L * = 59.9, a * = 3.0 and b * = 30.3. If you leave a hydrocarbon under otherwise identical conditions z. B. acetylene with flow rates of, for example, 0.25 and 0.50 cm 3 / min. one, one obtains for the deposited titanium nitride Layers of color coordinates of L * = 55.7, a * = 5.8 and b * = 30.3 or L * = 55.0, a * = 7.5 and b * = 25.4. The increase in the red value a * with carbon additions during the titanium nitride deposition without changing the yellow value b * is significant in the former case. However, the example also makes it clear that under otherwise specified process conditions there is a maximum hydrocarbon addition above which the yellowness index begins to decrease.

Claims

Verfahren zur Verbesserung des Farbeindrucks von Titannitrid-Schichten Patentansprüche Process for improving the color impression of titanium nitride layers 1. Verfahren zur Verbesserung des Farbeindrucks von1. Process for improving the color impression of Titannitrid-Schichten mittels plasmagestützter Beschichtungsmethoden, insbesondere mittels Magnetronsputtern, unter Verwendung eines Prozeßgases aus einem Edelgas und Stickstoff, dadurch gekennzeichnet, daß in den Reaktiαnsraum zwischen einem Target und einem zu beschichtenden Substrat Kohlenstoff eingebracht wird, und daß die Beschichtung bei Substrattemperaturen: von weniger als 250°C durchgeführt wird und daß die Gebrauchseigenschaften der Schicht über die Substrattemperatur und Biasspannung und der Farbeindruck über den Kohlenstoffanteil eingestellt werden.Titanium nitride layers by means of plasma-supported coating methods, in particular by means of magnetron sputtering, using a process gas consisting of an inert gas and nitrogen, characterized in that carbon is introduced into the reaction space between a target and a substrate to be coated, and that the coating at substrate temperatures: less than 250 ° C is carried out and that the properties of the layer are adjusted via the substrate temperature and bias voltage and the color impression via the carbon content. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Beschichtung bei Substrattemperaturen von 20 bis 200°C, vorzugsweise 150°C, durchgeführt wird.2. The method according to claim 1, characterized in that the coating is carried out at substrate temperatures of 20 to 200 ° C, preferably 150 ° C. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Biasspannung 50 bis 200 V, vorzugsweise 80 bis 150 V, beträgt. 3. The method according to claim 1 or 2, characterized in that the bias voltage is 50 to 200 V, preferably 80 to 150 V. 4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß in den Reaktionsraum gesättigte oder ungesättigte substituierte oder unsubstituierte Kohlenwasserstoffe mit 1 bis 6, vorzugsweise 1 bis 3 C-Atomen eingeleitet werden.4. The method according to any one of claims 1 to 3, characterized in that saturated or unsaturated substituted or unsubstituted hydrocarbons having 1 to 6, preferably 1 to 3, carbon atoms are introduced into the reaction space. 5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß als Kohlenwasserstoff Acetylen eingeleitet wird.5. The method according to any one of claims 1 to 4, characterized in that acetylene is introduced as the hydrocarbon. 6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Kohlenwasserstoffe ab etwa der Mitte der gesamten Beschichtungszeit oder gegen Ende der Beschichtung zugeführt werden.6. The method according to any one of claims 1 to 5, characterized in that the hydrocarbons are supplied from about the middle of the total coating time or towards the end of the coating. 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Durchflußmenge des Kohlenwasserstoffs kontinuierlich gesteigert wird.7. The method according to any one of claims 1 to 6, characterized in that the flow rate of the hydrocarbon is continuously increased. 8. Verfahren nach einem der Ansprüche 1 bis dadurch gekennzeichnet, daß die Durchflußmenge des KohlenWasserstoffs 0,05 bis 1 cm3/Min. beträgt.8. The method according to any one of claims 1 to characterized in that the flow rate of the hydrocarbon 0.05 to 1 cm 3 / min. is. 9. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Target aus Titancarbid besteht.9. The method according to any one of claims 1 to 3, characterized in that the target consists of titanium carbide. 10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß ab etwa der Mitte der gesamten Beschichtungszeit oder gegen Ende der Beschichtung die Durchflußmenge des Stickstoffs kontinuierlich verändert wird. 10. The method according to claim 9, characterized in that from about the middle of the total coating time or towards the end of the coating, the flow rate of the nitrogen is continuously changed. 11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Biasspannung während der Beschichtung, vorzugsweise stetig, geändert wird. 11. The method according to any one of claims 1 to 10, characterized in that the bias voltage during the coating, preferably continuously, is changed.
PCT/EP1985/000324 1984-07-11 1985-07-04 Method for improving the colour effect of titanium nitride layers Ceased WO1986000649A1 (en)

Applications Claiming Priority (2)

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DEP3425467.6 1984-07-11
DE19843425467 DE3425467A1 (en) 1984-07-11 1984-07-11 METHOD FOR IMPROVING THE COLOR IMPRESSION OF TITAN NITRIDE LAYERS

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EP0413853A1 (en) * 1989-08-21 1991-02-27 Balzers Aktiengesellschaft Workpiece coated with a solid solution crystalline layer, process and apparatus for its manufacture
DE4020595A1 (en) * 1990-06-28 1992-01-09 Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh Electric reflector lamp for accent lighting
CN108505004A (en) * 2018-05-04 2018-09-07 武汉理工大学 Stainless steel knife preparation method with chromatic colour TiN coatings

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* Cited by examiner, † Cited by third party
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AU645758B2 (en) * 1989-08-21 1994-01-27 Balzers Aktiengesellschaft Workpiece coated with a solid solution layer, method for its production, use of the workpiece, and apparatus for carrying out the method
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CN108505004A (en) * 2018-05-04 2018-09-07 武汉理工大学 Stainless steel knife preparation method with chromatic colour TiN coatings

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