DE2649685A1 - Chemical vapour deposition onto substrates such as tool sheet - using two vessels so substrate is kept below gas reaction temp. - Google Patents

Chemical vapour deposition onto substrates such as tool sheet - using two vessels so substrate is kept below gas reaction temp.

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Publication number
DE2649685A1
DE2649685A1 DE19762649685 DE2649685A DE2649685A1 DE 2649685 A1 DE2649685 A1 DE 2649685A1 DE 19762649685 DE19762649685 DE 19762649685 DE 2649685 A DE2649685 A DE 2649685A DE 2649685 A1 DE2649685 A1 DE 2649685A1
Authority
DE
Germany
Prior art keywords
substrate
reaction
vessels
vapour deposition
chemical vapour
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.)
Withdrawn
Application number
DE19762649685
Other languages
German (de)
Inventor
Rolf Hoeller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DOERRENBERG EDELSTAHL GmbH
Original Assignee
DOERRENBERG EDELSTAHL GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DOERRENBERG EDELSTAHL GmbH filed Critical DOERRENBERG EDELSTAHL GmbH
Priority to DE19762649685 priority Critical patent/DE2649685A1/en
Publication of DE2649685A1 publication Critical patent/DE2649685A1/en
Withdrawn legal-status Critical Current

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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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4481—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material

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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)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The substrate is located in a vessel (2) which is separated from the reaction vessel (1). The two vessels (1,2) are connected to each other, but the substrate is held at a temp lower than the reaction temp. of the gases in vessel (1). The reaction of the gases pref. occurs in a stream of carrier gas; and the pref. starting materials are metal acetyl-acetones; metal carbonyls; or metal halides. Tools made of high speed steel or a sec.-hardened, ledeburitic chromium steel can be surface hardened to over 60 HRc with TiC at 500 degrees C., i.e. below the normal tempering temp. for these steels.

Description

Beschichtungsverfahren Coating process

Die Erfindung betrifft das an sich bekannte Dampfabscheidungsverfahren (CVD-Verfahren=chemical vapor deposition), bei welchem unter Wärmeeinwirkung gasförmige Ausgangsstoffe zersetzt und miteinander zur Reaktion gebracht werden, wobei sich das gebildete feste Reaktionsprodukt dann auf einem in dem Reaktionsraum befindlichen Substrat, z.B. einem zu beschichtenden Werkzeug oder Bauteil, niederschlägt. Dabei befindet sich das zu beschichtende Substrat im Reaktionsraum, d.h., seine Temperatur ist mindestens gleich der Reaktionstemperatur.The invention relates to the vapor deposition process known per se (CVD process = chemical vapor deposition), in which gaseous under the action of heat Starting materials are decomposed and reacted with each other, whereby the solid reaction product formed then on a located in the reaction space The substrate, e.g. a tool or component to be coated, precipitates. Included is the substrate to be coated in the reaction space, i.e. its temperature is at least equal to the reaction temperature.

Das verhindert die Anwendung dieses Verfahrens auf Substrate aus solchen Materialien, welche die erforderlichen Reaktionstemperaturen nicht ohne unerwünschte Veränderungen aushalten.This prevents the application of this method to substrates made from such Materials that do not reach the required reaction temperatures without undesired Withstand change.

Die vorliegende Erfindung ermöglicht nun die Durchführung des Verfahrens bei niedrigeren Substrattemperaturen als die Reaktionstemperatur, was dadurch ermöglicht wird, daf3 man das Substrat in einem von dem Reaktionsraum getrennten, jedoch mit diesem in Verbindung stehenden Raum anordnet, in welchemdas Substrat auf einer unter der Reaktionstemperatur liegenden Temperatur gehalten wird.The present invention now enables the method to be carried out at lower substrate temperatures than the reaction temperature, which thereby enables is that the substrate is in a separate from the reaction space, but with this communicating space in which the substrate is placed on a lower the temperature lying at the reaction temperature is maintained.

Zweckmäßig erfolgt die Überführung der Reaktionsprodukte aus dem Reaktionsraum in den Beschichtungsraum mit Hilfe eines inerten Trägergases.The reaction products are expediently transferred from the reaction space into the coating room with the aid of an inert carrier gas.

Auf diese Weise gelingt es z.B., Schnellarbeitsstahl-Werkzeuge bzw. Werkzeuge aus sekundärhärtenden ledeburitischen Ghromstählen bei Temperaturen um 5000C, also unter halb der normalerweise üblichen Anlaßtemperaturen zur Einstellung einer Einbauhärte> 60 HRc mit TiC zu bescliichten.In this way, it is possible, for example, to use high-speed steel tools or Tools made of secondary hardening ledeburitic chromium steels at temperatures around 5000C, so below half the normally usual tempering temperatures for setting an installation hardness> 60 HRc with TiC.

Nach dem Verfahren gemäß der Erfindung können z.B. Beschichtungen aus Nickel, Kupfer, Chrom, Titan, Molybdän, Wolfram oder auch Karbid-, Nitrid- und Oxidbeschichtungen erhalten werden. Diese Beschichtungen oder deren Kombinationen (Sandlfich-Schicht) werden durch Zersetzen und Reaktion von Metall-Acetylacetonaten, -carbonylen und -halogeniden hergestellt.For example, coatings made of nickel, copper, chromium, titanium, molybdenum, tungsten or carbide, nitride and Oxide coatings can be obtained. These coatings or their combinations (Sandlfich layer) are formed by the decomposition and reaction of metal acetylacetonates, carbonyls and halides.

Beispielsweise können die folgenden Reaktionen genutzt werden. Der jeweils auf der rechten Seite mit genannte Stoff wird dabei auf dem Substrat, z.B. dem Werkzeug oder Bauteil, abgeschieden, wobei die Substrattemperatur im Sinne der Erfindung unterhalb der angegebenen Reaktionstemperatur liegt. For example, the following reactions can be used. The substance mentioned in each case on the right-hand side is deposited on the substrate, for example the tool or component, the substrate temperature in the context of the invention being below the specified reaction temperature.

8000C < T < 10000C 2 TaCl + 5 H + N > 2 -T + + 10 HCI 1000°C < T 1000 0 < T < 1500 0 3 Tal5 + 5 NfI3 » Ta3I\< + 15 HCl 0 0 gooOc 1300 0 2 TaCl5 + 5 H2 + 02 -~> 2 6-TaOt + 10 HOI T-= 6000C + TaC1 + J K, i 2,5 0, -3 Tn20,r5/ + 10 HCl 2 TaCl5 + 5 H2 + 2,5 02 Ta205 T = 7000C Co (c H 02)2 + Wasserstoff > com( + Aceton + Kohlenwasser- T = 3500C Al (C5 H7 02)2 + Wasserstoff --E Al-Oxid; + Aceton + Kohlen- wasserstoffe T = 4000C 2 TiC13 + 3 H2 ~~> 2 Ti; + 6 HCl T = 9000C Ti C14 + 2 I12 ^ Tiß + 4 HCl T = 9000C 2 MoCl5 + 5 H2 z 2 Moß + 10 HCl T = 8000C WCl6 + 3 H2 ) WW + 6 HCl T = 9000C WF6 + 3 H2 I W + 6 HF T=10000C 2 TiOl4 + 4 H2 + N2 ~~1 2 TiNl + 8 HOl T = 900°C TiCl4 + Wasserstoff + Methan -> TiC; + HOl T = 9000C TiC14 + 2 H2 + °2 > TiO2 + 4 HOl T = 90000 Die Zeichnung erläutert in schematischer Darstellung die Durchführung des erfindungsgemäßen Verfahrens: Mit 1 ist ein Reaktionstiegel dargestellt, wie er üb]icherweise bei den bekannten CVD-Verfahren verwendet wird. Die darin gebildeten Reaktionsprodukte strömen infolge des Temperaturgefälles in den auf niedrigerer Temperatur gehaltenen Beschichtungsraum 2, in welchen sich das zu beschich tende Substrat befindet.8000C <T <10000C 2 TaCl + 5 H + N> 2 -T + + 10 HCl 1000 ° C <T. 1000 0 <T <1500 0 3 Tal5 + 5 NfI3 »Ta3I \ <+ 15 HCl 0 0 gooOc 1300 0 2 TaCl5 + 5 H2 + 02 - ~> 2 6-TaOt + 10 HOI T- = 6000C + TaC1 + JK, i 2.5 0, -3 Tn20, r5 / + 10 HCl 2 TaCl5 + 5 H2 + 2.5 02 Ta205 T = 7000C Co (c H 02) 2 + hydrogen> com (+ acetone + hydrocarbon T = 3500C Al (C5 H7 02) 2 + hydrogen --E Al oxide; + Acetone + carbon hydrogen T = 4000C 2 TiC13 + 3 H2 ~~> 2 Ti; + 6 HCl T = 9000C Ti C14 + 2 I12 ^ Tiß + 4 HCl T = 9000C 2 MoCl5 + 5 H2 z 2 Moß + 10 HCl T = 8000C WCl6 + 3 H2) WW + 6 HCl T = 9000C WF6 + 3 H2 IW + 6 HF T = 10000C 2 TiOl4 + 4 H2 + N2 ~~ 1 2 TiNl + 8 HOl T = 900 ° C TiCl4 + hydrogen + methane ->TiC; + HOl T = 9000C TiC14 + 2 H2 + ° 2> TiO2 + 4 HOl T = 90000 The drawing explains the implementation of the method according to the invention in a schematic representation: 1 shows a reaction crucible such as is usually used in the known CVD methods. The reaction products formed therein flow as a result of the temperature gradient into the coating chamber 2, which is kept at a lower temperature and in which the substrate to be coated is located.

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Claims (3)

Patentansrüche 1) Verfahren zur Beschichtung von insbesondere metallischen Substraten durch chemisches Bedampfen, wobei in einem Reaktionsraum durch Reaktion in der Gasphase das abzuscheidende Material gebildet wird und sich darni auf dem Substrat niederschlägt, dadurch gekennzeichnet, daß sich das Substrat in einem von dem Reaktionsraum getrennten, jedoch mit diesem in Verbindung stehenden Raum befindet und auf einer Temperatur unterhalb der Reaktionstemperatur gehalten wird. Claims 1) Process for coating, in particular metallic Substrates by chemical vapor deposition, whereby in a reaction chamber by reaction in the gas phase the material to be deposited is formed and darni on the Deposits substrate, characterized in that the substrate is in one of the reaction space is separate, but connected to this space and is kept at a temperature below the reaction temperature. 2) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Reaktion in einem Trägergasstrom erfolgt.2) Method according to claim 1, characterized in that the reaction takes place in a carrier gas stream. 3) Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als Ausgangsstoffe für die Reaktion Metall-Acetylacetonate, Metallcarbonyle oder Metallhalogenide verwendet werden.3) Method according to claim 1 or 2, characterized in that as Starting materials for the reaction of metal acetylacetonates, metal carbonyls or metal halides be used.
DE19762649685 1976-10-29 1976-10-29 Chemical vapour deposition onto substrates such as tool sheet - using two vessels so substrate is kept below gas reaction temp. Withdrawn DE2649685A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19762649685 DE2649685A1 (en) 1976-10-29 1976-10-29 Chemical vapour deposition onto substrates such as tool sheet - using two vessels so substrate is kept below gas reaction temp.

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Application Number Priority Date Filing Date Title
DE19762649685 DE2649685A1 (en) 1976-10-29 1976-10-29 Chemical vapour deposition onto substrates such as tool sheet - using two vessels so substrate is kept below gas reaction temp.

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DE2649685A1 true DE2649685A1 (en) 1978-05-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2545984A1 (en) * 1983-05-11 1984-11-16 Semiconductor Res Found METHOD FOR DRY FABRICATION OF A SEMICONDUCTOR DEVICE BY PHOTOCHEMICAL REACTION AND APPARATUS FOR CARRYING OUT SAID METHOD

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2545984A1 (en) * 1983-05-11 1984-11-16 Semiconductor Res Found METHOD FOR DRY FABRICATION OF A SEMICONDUCTOR DEVICE BY PHOTOCHEMICAL REACTION AND APPARATUS FOR CARRYING OUT SAID METHOD

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