WO1996018756A1 - A PA-CVD PROCESS FOR DEPOSITION OF A SOLID METAL-CONTAINING FILM ONTO A SUBSTRATE CONTAINING AT LEAST 50 % of Fe or WC - Google Patents

A PA-CVD PROCESS FOR DEPOSITION OF A SOLID METAL-CONTAINING FILM ONTO A SUBSTRATE CONTAINING AT LEAST 50 % of Fe or WC Download PDF

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Publication number
WO1996018756A1
WO1996018756A1 PCT/DK1995/000505 DK9500505W WO9618756A1 WO 1996018756 A1 WO1996018756 A1 WO 1996018756A1 DK 9500505 W DK9500505 W DK 9500505W WO 9618756 A1 WO9618756 A1 WO 9618756A1
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Prior art keywords
metal
metal halide
gas
film
process gas
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PCT/DK1995/000505
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French (fr)
Inventor
Kristian GLEJBØL
Nini Hamawi Pryds
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Nkt Research Center A/S
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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
    • 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
    • C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • 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
    • C23C16/32—Carbides
    • 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

Definitions

  • the present invention is directed to a plasma assisted chemical vapour deposition (PA-CVD) process for deposition of a solid metal-containing film onto the surface of a sub ⁇ strate containing at least 50% of Fe or WC, by which the me ⁇ tallic component of the solid metal-containing film is in- troduced into the system as a metal halide.
  • PA-CVD plasma assisted chemical vapour deposition
  • a CVD process is commonly defined as a chemical reaction of gaseous film-forming compounds close to, or on a surface, resulting in solid deposits and volatile waste products. Most often the reaction takes place in a closed vessel in order to avoid contamination from the ambient atmosphere. To promote the reactions, activation of the gas is often neces ⁇ sary * The methods of activation includes heating of the gas (thermal activation) and excitation of the gas by electric fields (plasma activation). Often a combination of different excitation methods is used. When excitation of the gas by electrical fields is employed, the process is normally re ⁇ ferred to as plasma assisted chemical vapour deposition (PA- CVD).
  • PA- CVD plasma assisted chemical vapour deposition
  • T1C1 2 is an important precursor for the synthesis of TiN from TiCl 4 , N 2 and H 2 .
  • T1C1 2 is believed to be formed in the free gas according to the reduction reaction TiCl 4 + H 2 -> T1C1 2 + 2HC1. After formation the TiCl 2 molecules diffuse to the sur ⁇ face.
  • Kazuki Kawata describes in Surface and Coatings Technology, Vol. 54/55 (1992), pp. 604-608 CVD processes for deposition of TiN, TiC and Ti(C,N) films on steel substrates and CVD equipment suitable for mass-productional operation.
  • this gas composition is contacted with a substrate surface at a pressure of 1.3 to 1.3 x 10 3 Pa and a temperature of 573 to 873 K.
  • we have found that the TiN film formed according to these process parame ⁇ ters often suffers from Cl-contamination and insufficient adherence of the deposited film to the substrate.
  • W.A. Bryant describes in Journal of Crystal Growth Vol. 35, 1976, pp. 257-261 a CVD process for deposition of tungsten coatings according to the reaction WF 6 + 3H 2 -> W + 6HF.
  • deposits of uniform thickness are obtained by pulsing the WF 6 and H 2 gas pressure in the deposition cham ⁇ ber.
  • the process consists of intermit- tently injecting reactant gasses into a previously evacuated chamber.
  • deposition and evacuation periods of 10 seconds and 5 seconds, respec ⁇ tively, and 5800 cycle repetitions a W layer having a thickness of 0,75 mm is deposited.
  • US-A-5 279 857 describes a thermally activated CVD process for forming titanium nitride films on silicon substrates.
  • the purpose of this invention is to lower the Cl-content in the film and hence reduce its resistivity.
  • This process in ⁇ cludes two steps: In the first step a TiN film is deposited on the silicon substrate by passing both TiCl 4 and NH 3 gas into the reaction chamber.
  • the second step is a subsequent post-annealing step in which NH 3 gas only is passed into the reaction chamber in order to remove residual chlorine atoms retained by the deposited TiN film.
  • thermally activated CVD depo ⁇ sition of hard ceramic coatings such as TiN, TiC and A1 2 0 3 on hard metal (most often WC/Co composits) and HSS (High Speed Steel) is well-known in the art.
  • thermally acti ⁇ vated CVD is vitiated by the drawback that the substrate normally is heated to a temperature above 850°C. This may result in embrittlement of the hard metal substrates and softens the steel substrate.
  • softening of steel substrates is a problem, as hardened steels have to be rehardened after coating.
  • a PA-CVD process can be applied for deposit- ing hard ceramic coating on the above-mentioned substrates, since plasma activation allows the use of a lower deposition temperature.
  • plasma activation allows the use of a lower deposition temperature.
  • PA-CVD tecniques it has been found that the adherence of films deposited by PA-CVD tecniques is often too low for high performance applications.
  • this object is accomplished by a PA-CVD process which is characterized in that it comprises the following steps a) to c):
  • a second process gas essentially composed of: a metal halide, a diluent gas, a reduction agent, a non- metal precursor or any mixture thereof, the mole fraction of metal halide in this second process gas being substantially lower than the mole fraction of metal halide in the process gas used in step a);
  • metal-containing film covers pure metal films, pure ce- ramie films and metal films containing any amount of non- metal elements, including metal films in which a concentra ⁇ tion gradient of non-metal elements is present such as in a nitrided layer.
  • ceramic refers to materials com- prising both metallic and non-metallic elements.
  • non-metal precursor is defined as a gaseous starting com ⁇ pound providing the non-metallic element required for the formation of a ceramic film or a metal film containing non- metal elements during a CVD process. When e.g. TiC is formed from TiCl 4 and CH 4 , the latter compound is regarded as a non- metal precursor according to the above definition.
  • the present invention is based on the recog- nition that an improved adherence of the deposited film to the substrate can be achieved by shifting the process gas composition between a high and a low metal halide level.
  • the content of metal halide in the second process gas is substantially lower than the content of metal halide in the first process gas. More specifically the content of metal halide in the second process gas should be so low that the amount of unwanted halogen in the resulting film is reduced in comparison with films produced by prior art CVD tech- niques involving introduction of metal halides.
  • the mole fraction of metal halide in the process gas used in step b) is preferably 0 to 0.5 times, more preferably 0 to 0.1 times, the mole fraction of metal halide in the process gas used in step a).
  • the process gas used in step b) contains essentially no metal halide.
  • step a) may differ from time to time during the repetition of these steps.
  • the first process gas used in step a) is preferably fed for 1 to 1000 seconds, more preferably for 25 to 250 seconds.
  • the second process gas used in step b) should be fed for a time interval sufficiently long for a reduction of the halo ⁇ gen-content of the deposit formed in step a) to a desired level to occur. It is preferably fed for 1 to 5000 seconds, more preferably for 10 to 3600 seconds, and even more pref ⁇ erably for 60 to 1800 seconds
  • the process gases used in the above-mentioned steps a) and b) essentially contain no non-metal precursors.
  • a non-metal precursor should always be present either in the process gas of step a) or in the process gas of step b) or in both.
  • metal halide naturally depends on the desired constitution of the deposited metal-containing film.
  • the metal halide furthermore contains halogen atoms such as F, Cl and Br, preferably Cl.
  • the process gas can contain two or more metal halides simultaneously. In this way it is pos ⁇ sible to deposit e.g. metal alloy films and ceramic films comprising two or more metallic components.
  • non-metal precursor in case of deposition of ceramic films or metal films containing non-metal elements depends on the desired chemical constitution of the film.
  • N 2 and NH 3 are examples of suitable non-metal precursors for the deposition of nitrogen-containing ceramic or metal films.
  • CH 4 is an example of a suitable non-metal precursor for the deposition of carbon-containing ceramic or metal films.
  • the process gas can contain two or more different non-metal pre- cursors. Process gases containing two or more non-metal pre ⁇ cursors can e.g. be used for deposition of ceramic films comprising two or more non-metallic components.
  • Suitable reduction agents are those capable of reducing the metal halide of the process gas.
  • H 2 , CH 4 , NH 3 and CH 3 CN are the preferred reduction agents.
  • the diluent gas is preferably a noble gas such as argon or helium.
  • the above-mentioned steps a) and b) are repeated until a film of the desired thickness is formed on the substrate.
  • the said steps are preferably repeated at least once, more preferably 1 to 100 times, even more preferably 1 to 5 times.
  • the thickness of the film may be varied between very wide limits depending a.o. on the desired properties of the film (including tribological properties) which of course de ⁇ pend on the end use of the product.
  • the preferred thickness is between 0.1 and 100 ⁇ m.
  • the film thickness can be measured on a cross-section of the substrate either by optical microscopical methods or by electron microscopical methods. Numerous alternative methods are however available, and may be utilized as well.
  • a PA-CVD process for depositing a ceramic film or a metal film con ⁇ taining non-metal elements onto the surface of a substrate containing at least 50% Fe or WC, the process being charac- terized in that it comprises the steps of
  • a second process gas essentially composed of: a metal halide, a diluent gas, a reduction agent or any mix ⁇ ture thereof, the mole fraction of metal halide in this process gas being substantially lower than the mole fraction of metal halide in the process gas used in step a);
  • a third process gas essentially composed of: a non-metal precursor, or a non-metal precursor in combination with a reduction agent, a diluent gas or any mixture thereof;
  • steps a) to c) of this embodiment a metal layer with a low level of halogen contamination is deposited on the sub- strate.
  • this metal layer is reacted with a non- metal precursor resulting in the formation of a layer of ce ⁇ ramic or a layer of metal containing non-metal elements (e.g. a nitrided layer).
  • steps a) to d) are repeated until a ceramic film or a metal film containing non-metal elements of the desired thickness has been formed.
  • the third process gas used in step d) should be fed for a time interval sufficiently long for a reaction to a desired extent (e.g. a desired concentration gradient) between the metal film formed during steps a) to c) and the non-metal precursor to occur.
  • the time intervals actually used depend also of the thickness of the metal film formed during steps a) to c).
  • the third process gas is preferably fed for a time interval of 0.01 to 100, more prefarably 0.1 to 10 times, the total time used during steps a) to c).
  • the metal film formed as a result of steps a) to c) is completely transfor- med into a ceramic film in step d).
  • the metal film should be so thin that the entire metal film can be re ⁇ acted with the non-metal precursor in step d).
  • the preferred thickness of the metal film for complete transformation is 10 to 2000 nm.
  • the PA-CVD process of the invention (also referred to as "the pulsed PA-CVD process” ) is optionally followed by an ordinary continuous PA-CVD process. This may in particular be advantageuos when the problem of insufficient adherence is caused primarily by the presence of halogen contaminants at the film/substrate interface.
  • This process is preferably carried out by using a continuously fed process gas composed of:
  • a non-metal precursor 0 to 30 % of a non-metal precursor, 1 to 98 % of a reduction agent, the balance being a diluent gas.
  • An equipment normally used for thermal activated CVD con- sists in general of three main parts: a gas supply system, a heated vessel and a vacuum pump.
  • the gas mixture is lead into the heated vessel, which is pumped to the desired pressure utilized for the CVD reac ⁇ tions. From the pump the waste gasses can be bubbled through a scrubber to neutralize hazardous waste products formed during operation of the equipment.
  • the process gas is preferably activated by combining heating of the vessel (thermal activation) and excitation of the gas by electric fields (plasma activation).
  • the process according to the invention is of the type normally referred to as plasma assisted chemical vapour deposition (PA-CVD) .
  • the applied electric field may be either of the DC, low fre ⁇ quency AC or RF type. When the deposited film is a poor electrical conductor, an RF electric field is preferred.
  • the gas pressure is suitably selected according to the fol ⁇ lowing principles: If the gas pressure is too low, the plasma will extinguish. If on the other hand the gas pres ⁇ sure is too high, sparks may form between the electrodes.
  • the gas pressure in the vessel is between 0.1 and 10 mbar during the entire PA-CVD process.
  • the vessel temperature is suitably between ambient tempera ⁇ ture and 1500°C.
  • the vessel used in all examples is a cylinder having a di ⁇ ameter of approximately 150 mm and a height of 500 mm. Only the upper 350 mm of the vessel is heated.
  • the gasses are in- troduced into the vessel through a distributor made from a steel tube with numerous small holes, all located near the top of the reactor vessel.
  • the vessel is pumped through a hole in the bottom.
  • the specimens are placed on a holder lo ⁇ cated 300 mm from the bottom of the vessel.
  • the chlorine content of the formed films is measured by En ⁇ ergy Dispersive X-ray analysis (EDX) or Secondary Ion Mass Spectroscopy (SIMS).
  • EDX En ⁇ ergy Dispersive X-ray analysis
  • SIMS Secondary Ion Mass Spectroscopy
  • the adherence of the formed films to the substrate is meas ⁇ ured using the test method developed by Daimler-Benz AG (VDI-richtline 3198, HRc adhesive test).
  • PA-CVD deposition of a titanium nitride film on a steel sub ⁇ strate using DC plasma excitation PA-CVD deposition of a titanium nitride film on a steel sub ⁇ strate using DC plasma excitation.
  • the substrate was placed on a holder in the vessel.
  • the ves- sel was heated to 500 °C and a gas composed of 70% H 2 and 30%
  • Ar was fed into the vessel.
  • a DC voltage of 550V was applied in order to create a H 2 /Ar plasma.
  • the H 2 /Ar plasma was main ⁇ tained for 60 minutes in order to clean the substrate sur ⁇ face.
  • the gas composi ⁇ tion was varied by repeating the following gas composition sequence four times:
  • This gas composition sequence resulted in the formation of a Ti rich layer at the substrate surface.
  • the total gas pressure in the vessel was kept at approxi ⁇ mately 1 mbar and the vessel temperature was kept at 500 °C during the entire operation.
  • a TiN film having a thickness of 1 ⁇ m and containing essen ⁇ tially no Cl contaminants in the interface between the sub ⁇ strate and the TiN film was produced according to this exam ⁇ ple.
  • the substrate was placed on a holder in the vessel.
  • the ves ⁇ sel was heated to 750 °C and a gas composed of 70% H 2 and 30% Ar was fed into the vessel.
  • An RF electric field (frequency:13.56 MHz, power: 50 W) was applied in order to create a H 2 /Ar plasma.
  • the H 2 /Ar plasma was maintained for 60 minutes in order to clean the substrate surface.
  • the gas composi ⁇ tion was varied by constantly repeating the following gas composition sequence 50 times:
  • the total gas pressure in the vessel was kept at approxi ⁇ mately 0.5 mbar and the vessel temperature was kept at 750 °C during the entire operation.
  • Example 2 This Example was carried out as described in Example II with the exception that a process gas having the following compo ⁇ sition was continuously fed into the vessel:
  • the substrate was placed on a holder in the vessel.
  • the ves ⁇ sel was heated to 500 °C and a gas composed of 70% H 2 and 30% Ar was fed into the vessel.
  • a RF electric field (frequency:13.56 MHz, power: 100 W) was applied in order to create a H 2 /Ar plasma.
  • the H 2 /Ar plasma was maintained for 60 minutes in order to clean the substrate surface.
  • the gas composi ⁇ tion was varied by constantly repeating the following gas composition sequence for a period of 60 minutes:
  • the total gas pressure in the vessel was kept at approxi ⁇ mately 0.4 mbar and the vessel temperature was kept at 750 °C during the entire operation.
  • Example III This Example was carried out as described in Example III with the exception that a process gas having the following composition was continuously fed into the vessel:

Abstract

A new plasma assisted chemical vapour deposition (PA-CVD) process for deposition of a solid metal-containing film onto the surface of a substrate containing at least 50 % of Fe or WC (such as hard metal or steel), by which the metallic component of the metal-containing film is introduced into the system as a metal halide, is disclosed. The new process involves shifting the process gas composition between a high and a low metal halide level, whereby the adhesion of the deposited film to the substrate is improved.

Description

A PA-CVD process for deposition of a solid metal containing film onto a substrate containing at least 50% of Fe or WC
The present invention is directed to a plasma assisted chemical vapour deposition (PA-CVD) process for deposition of a solid metal-containing film onto the surface of a sub¬ strate containing at least 50% of Fe or WC, by which the me¬ tallic component of the solid metal-containing film is in- troduced into the system as a metal halide.
A CVD process is commonly defined as a chemical reaction of gaseous film-forming compounds close to, or on a surface, resulting in solid deposits and volatile waste products. Most often the reaction takes place in a closed vessel in order to avoid contamination from the ambient atmosphere. To promote the reactions, activation of the gas is often neces¬ sary* The methods of activation includes heating of the gas (thermal activation) and excitation of the gas by electric fields (plasma activation). Often a combination of different excitation methods is used. When excitation of the gas by electrical fields is employed, the process is normally re¬ ferred to as plasma assisted chemical vapour deposition (PA- CVD).
Although the reaction resulting in the solid deposit has to run at or near the surface, precursors important to this re¬ action are often formed in the gas phase. As an example, T1C12 is an important precursor for the synthesis of TiN from TiCl4, N2 and H2. T1C12 is believed to be formed in the free gas according to the reduction reaction TiCl4 + H2 -> T1C12 + 2HC1. After formation the TiCl2 molecules diffuse to the sur¬ face.
A wide range of materials may be deposited on a surface by CVD. Below are given a few important examples: SiH4 + 2C02 -> Si02 ( BOlid) + 2C0 + 2H2
CH4 -> C( Bolid ) + 2H2
TiCl4 + CH4 -> TiC( solid) + 4HC1
2TiCl4 + 4H2 + N2 -> 2TiN( βolid) + 8HC1
In the above reaction schemes, formulae on the left-hand side of the arrows represent gaseous film-forming compounds and formulae on the right-hand side of the arrows represent the resulting deposits (indicated by the subindex "solid") and volatile waste gases.
Prior art techniques for CVD deposition of metal-containing films are often vitiated by the drawback that the solid de- posit and/or the interface between the substrate and the de¬ posit is contaminated by adsorbed waste gas and/or film- forming precursors. Thus, CVD processes for the deposition of metal-containing films by which the metallic component of the deposit is introduced into the system as a metal halide often result in halogen-contaminated films.
Kazuki Kawata describes in Surface and Coatings Technology, Vol. 54/55 (1992), pp. 604-608 CVD processes for deposition of TiN, TiC and Ti(C,N) films on steel substrates and CVD equipment suitable for mass-productional operation. As an example of a gas composition suitable for TiN film coating the following is mentioned: N2:Ar:H2:TiCl4 = 18.8:4:75:2.2. During a PA-CVD process this gas composition is contacted with a substrate surface at a pressure of 1.3 to 1.3 x 103 Pa and a temperature of 573 to 873 K. However, we have found that the TiN film formed according to these process parame¬ ters often suffers from Cl-contamination and insufficient adherence of the deposited film to the substrate.
W.A. Bryant describes in Journal of Crystal Growth Vol. 35, 1976, pp. 257-261 a CVD process for deposition of tungsten coatings according to the reaction WF6 + 3H2 -> W + 6HF. In this process deposits of uniform thickness are obtained by pulsing the WF6 and H2 gas pressure in the deposition cham¬ ber. More specifically the process consists of intermit- tently injecting reactant gasses into a previously evacuated chamber. By using nominal pressures during deposition and evacuation of 15 Torr and 2 Torr, respectively, deposition and evacuation periods of 10 seconds and 5 seconds, respec¬ tively, and 5800 cycle repetitions, a W layer having a thickness of 0,75 mm is deposited.
US-A-5 279 857 describes a thermally activated CVD process for forming titanium nitride films on silicon substrates. The purpose of this invention is to lower the Cl-content in the film and hence reduce its resistivity. This process in¬ cludes two steps: In the first step a TiN film is deposited on the silicon substrate by passing both TiCl4 and NH3 gas into the reaction chamber. The second step is a subsequent post-annealing step in which NH3 gas only is passed into the reaction chamber in order to remove residual chlorine atoms retained by the deposited TiN film.
For tribological applications thermally activated CVD depo¬ sition of hard ceramic coatings such as TiN, TiC and A1203 on hard metal (most often WC/Co composits) and HSS (High Speed Steel) is well-known in the art. However, thermally acti¬ vated CVD is vitiated by the drawback that the substrate normally is heated to a temperature above 850°C. This may result in embrittlement of the hard metal substrates and softens the steel substrate. Especially the softening of steel substrates is a problem, as hardened steels have to be rehardened after coating.
Alternatively, a PA-CVD process can be applied for deposit- ing hard ceramic coating on the above-mentioned substrates, since plasma activation allows the use of a lower deposition temperature. However, it has been found that the adherence of films deposited by PA-CVD tecniques is often too low for high performance applications.
Thus, it is an object of the present invention to provide a simple PA-CVD process for deposition of a solid metal-con¬ taining film onto the surface of a substrate containing at least 50% of Fe or WC by which the metallic component of the metal-containing film is introduced into the system as a metal halide and in which process the adhesion of the depos¬ ited film to the substrate is improved in comparison with films produced by prior art PA-CVD techniques involving in¬ troduction of metal halides.
According to the invention this object is accomplished by a PA-CVD process which is characterized in that it comprises the following steps a) to c):
a) feeding a first process gas essentially composed of: a metal halide, or a metal halide in combination with a diluent gas, a reduc¬ tion agent, a non-metal precursor or any mixture thereof;
b) feeding a second process gas essentially composed of: a metal halide, a diluent gas, a reduction agent, a non- metal precursor or any mixture thereof, the mole fraction of metal halide in this second process gas being substantially lower than the mole fraction of metal halide in the process gas used in step a);
c) repeating steps a) and b) until a metal-containing film of the desired thickness has been formed.
In the present context semiconducting elements such as Si are included in the definition of metals. The expression
"metal-containing film" covers pure metal films, pure ce- ramie films and metal films containing any amount of non- metal elements, including metal films in which a concentra¬ tion gradient of non-metal elements is present such as in a nitrided layer. The term "ceramic" refers to materials com- prising both metallic and non-metallic elements. The term "non-metal precursor" is defined as a gaseous starting com¬ pound providing the non-metallic element required for the formation of a ceramic film or a metal film containing non- metal elements during a CVD process. When e.g. TiC is formed from TiCl4 and CH4, the latter compound is regarded as a non- metal precursor according to the above definition.
It is surprising that the presence of halogen-contaminants in films, in particular at the film/substrate interface, de- posited from metal halides is responsible for the inferior adherence of such films. Moreover it is unforeseen that the concentration of halogen contaminants in the resulting film and/or film/substrate interface can be reduced (and hence the adherence improved) in a simple and efficient manner without adversely affecting the properties of the film by varying the content of metal halide in the process gas in intervals during the CVD process.
In other words, the present invention is based on the recog- nition that an improved adherence of the deposited film to the substrate can be achieved by shifting the process gas composition between a high and a low metal halide level.
The content of metal halide in the second process gas is substantially lower than the content of metal halide in the first process gas. More specifically the content of metal halide in the second process gas should be so low that the amount of unwanted halogen in the resulting film is reduced in comparison with films produced by prior art CVD tech- niques involving introduction of metal halides. The mole fraction of metal halide in the process gas used in step b) is preferably 0 to 0.5 times, more preferably 0 to 0.1 times, the mole fraction of metal halide in the process gas used in step a).
In a particular preferred embodiment of the invention the process gas used in step b) contains essentially no metal halide.
The time intervals and gas compositions used in step a) as well as step b) may differ from time to time during the repetition of these steps.
The first process gas used in step a) is preferably fed for 1 to 1000 seconds, more preferably for 25 to 250 seconds.
The second process gas used in step b) should be fed for a time interval sufficiently long for a reduction of the halo¬ gen-content of the deposit formed in step a) to a desired level to occur. It is preferably fed for 1 to 5000 seconds, more preferably for 10 to 3600 seconds, and even more pref¬ erably for 60 to 1800 seconds
When the process of the invention is used for deposition of a pure metal film onto a substrate, the process gases used in the above-mentioned steps a) and b) essentially contain no non-metal precursors. When, on the other hand, the proc¬ ess of the invention is used for deposition of a ceramic film, a non-metal precursor should always be present either in the process gas of step a) or in the process gas of step b) or in both.
The choice of metal halide naturally depends on the desired constitution of the deposited metal-containing film. Metal halides containing a metal such as Al, Si or a transitional metal such as Ti, Cr, W, Mo, V, Hf and Ta, are preferred. The metal halide furthermore contains halogen atoms such as F, Cl and Br, preferably Cl. The process gas can contain two or more metal halides simultaneously. In this way it is pos¬ sible to deposit e.g. metal alloy films and ceramic films comprising two or more metallic components.
The choice of non-metal precursor in case of deposition of ceramic films or metal films containing non-metal elements depends on the desired chemical constitution of the film. N2 and NH3 are examples of suitable non-metal precursors for the deposition of nitrogen-containing ceramic or metal films. CH4 is an example of a suitable non-metal precursor for the deposition of carbon-containing ceramic or metal films. The process gas can contain two or more different non-metal pre- cursors. Process gases containing two or more non-metal pre¬ cursors can e.g. be used for deposition of ceramic films comprising two or more non-metallic components.
Suitable reduction agents are those capable of reducing the metal halide of the process gas. H2, CH4, NH3 and CH3CN are the preferred reduction agents.
The diluent gas is preferably a noble gas such as argon or helium.
The above-mentioned steps a) and b) are repeated until a film of the desired thickness is formed on the substrate. The said steps are preferably repeated at least once, more preferably 1 to 100 times, even more preferably 1 to 5 times. The thickness of the film may be varied between very wide limits depending a.o. on the desired properties of the film (including tribological properties) which of course de¬ pend on the end use of the product. The preferred thickness is between 0.1 and 100 μm. The film thickness can be measured on a cross-section of the substrate either by optical microscopical methods or by electron microscopical methods. Numerous alternative methods are however available, and may be utilized as well.
In an embodiment of the invention there is provided a PA-CVD process for depositing a ceramic film or a metal film con¬ taining non-metal elements onto the surface of a substrate containing at least 50% Fe or WC, the process being charac- terized in that it comprises the steps of
a) feeding a first process gas essentially composed of: a metal halide, or a metal halide in combination with a diluent gas, a reduc- tion agent or any mixture thereof;
b) feeding a second process gas essentially composed of: a metal halide, a diluent gas, a reduction agent or any mix¬ ture thereof, the mole fraction of metal halide in this process gas being substantially lower than the mole fraction of metal halide in the process gas used in step a);
c) repeating steps a) and b) until a metal film of a desired thickness has been formed;
d) feeding a third process gas essentially composed of: a non-metal precursor, or a non-metal precursor in combination with a reduction agent, a diluent gas or any mixture thereof; and
e) repeating steps a) to d) until a metal-containing film of a desired thickness has been formed.
In steps a) to c) of this embodiment a metal layer with a low level of halogen contamination is deposited on the sub- strate. In step d) this metal layer is reacted with a non- metal precursor resulting in the formation of a layer of ce¬ ramic or a layer of metal containing non-metal elements (e.g. a nitrided layer). Then steps a) to d) are repeated until a ceramic film or a metal film containing non-metal elements of the desired thickness has been formed.
The third process gas used in step d) should be fed for a time interval sufficiently long for a reaction to a desired extent (e.g. a desired concentration gradient) between the metal film formed during steps a) to c) and the non-metal precursor to occur. The time intervals actually used depend also of the thickness of the metal film formed during steps a) to c). The third process gas is preferably fed for a time interval of 0.01 to 100, more prefarably 0.1 to 10 times, the total time used during steps a) to c).
In a particular embodiment of the invention the metal film formed as a result of steps a) to c) is completely transfor- med into a ceramic film in step d). In this case the metal film should be so thin that the entire metal film can be re¬ acted with the non-metal precursor in step d). The preferred thickness of the metal film for complete transformation is 10 to 2000 nm.
The PA-CVD process of the invention (also referred to as "the pulsed PA-CVD process" ) is optionally followed by an ordinary continuous PA-CVD process. This may in particular be advantageuos when the problem of insufficient adherence is caused primarily by the presence of halogen contaminants at the film/substrate interface. This process is preferably carried out by using a continuously fed process gas composed of:
1 to 30 % of a metal halide,
0 to 30 % of a non-metal precursor, 1 to 98 % of a reduction agent, the balance being a diluent gas.
An equipment normally used for thermal activated CVD con- sists in general of three main parts: a gas supply system, a heated vessel and a vacuum pump.
From the gas supply system, operated at near ambient pres¬ sure, the gas mixture is lead into the heated vessel, which is pumped to the desired pressure utilized for the CVD reac¬ tions. From the pump the waste gasses can be bubbled through a scrubber to neutralize hazardous waste products formed during operation of the equipment.
Since pure thermal activation is not sufficient to promote the chemical reactions involved in the process according to the invention, additional energy is transferred to the gas by plasma excitation.
The process gas is preferably activated by combining heating of the vessel (thermal activation) and excitation of the gas by electric fields (plasma activation). Thus, the process according to the invention is of the type normally referred to as plasma assisted chemical vapour deposition (PA-CVD) . The applied electric field may be either of the DC, low fre¬ quency AC or RF type. When the deposited film is a poor electrical conductor, an RF electric field is preferred.
In order to obtain a proper plasma excitation of the gas, the gas pressure is suitably selected according to the fol¬ lowing principles: If the gas pressure is too low, the plasma will extinguish. If on the other hand the gas pres¬ sure is too high, sparks may form between the electrodes. Preferably the gas pressure in the vessel is between 0.1 and 10 mbar during the entire PA-CVD process. The vessel temperature is suitably between ambient tempera¬ ture and 1500°C.
In the following examples deposition of metal-containing films using the process of the invention is illustrated.
The vessel used in all examples is a cylinder having a di¬ ameter of approximately 150 mm and a height of 500 mm. Only the upper 350 mm of the vessel is heated. The gasses are in- troduced into the vessel through a distributor made from a steel tube with numerous small holes, all located near the top of the reactor vessel. The vessel is pumped through a hole in the bottom. The specimens are placed on a holder lo¬ cated 300 mm from the bottom of the vessel.
The chlorine content of the formed films is measured by En¬ ergy Dispersive X-ray analysis (EDX) or Secondary Ion Mass Spectroscopy (SIMS).
The adherence of the formed films to the substrate is meas¬ ured using the test method developed by Daimler-Benz AG (VDI-richtlinie 3198, HRc adhesive test).
Unless otherwise stated, all percentages given in the fol- lowing examples are percentages by mole.
EXAMPLE I
PA-CVD deposition of a titanium nitride film on a steel sub¬ strate using DC plasma excitation.
General reaction scheme:
2TiCl4 + N2 + 4H2 -> 2TiN + 8HC1
The substrate was placed on a holder in the vessel. The ves- sel was heated to 500 °C and a gas composed of 70% H2 and 30%
Ar was fed into the vessel. A DC voltage of 550V was applied in order to create a H2/Ar plasma. The H2/Ar plasma was main¬ tained for 60 minutes in order to clean the substrate sur¬ face.
Following the preliminary plasma cleaning, the gas composi¬ tion was varied by repeating the following gas composition sequence four times:
Feed time H2 (%) N2 (%) Ar (%) TiCl4 (%) (s)
60 50 0 48 2
240 50 0 50 0
This gas composition sequence resulted in the formation of a Ti rich layer at the substrate surface.
Then a gas having the following composition was fed into the vessel for a period of 1200 seconds:
H2 (%) N2 (%) Ar (%) TiCl4 (%)
40 20 40 0
This resulted in the formation of a TiN nitriding layer on the substrate surface.
Following the above steps, continuous deposition of TiN was carried out using a conventional constant gas flow scheme and a process gas having the following composition:
H2 (%) N2 (%) Ar (%) TiCl4 (%)
40 20 38 2 The continuous deposition was carried out for 60 minutes.
The total gas pressure in the vessel was kept at approxi¬ mately 1 mbar and the vessel temperature was kept at 500 °C during the entire operation.
A TiN film having a thickness of 1 μm and containing essen¬ tially no Cl contaminants in the interface between the sub¬ strate and the TiN film was produced according to this exam¬ ple.
EXAMPLE II
PA-CVD deposition of a silicon nitride film on a steel sub¬ strate using RF plasma excitation
General reaction scheme:
3SiH2Cl2 + 4NH3 -> Si3N4 + 6HC1 + 6H2
The substrate was placed on a holder in the vessel. The ves¬ sel was heated to 750 °C and a gas composed of 70% H2 and 30% Ar was fed into the vessel. An RF electric field (frequency:13.56 MHz, power: 50 W) was applied in order to create a H2/Ar plasma. The H2/Ar plasma was maintained for 60 minutes in order to clean the substrate surface.
Following the preliminary plasma cleaning, the gas composi¬ tion was varied by constantly repeating the following gas composition sequence 50 times:
Feed time NH3 (%) Ar (%) SiH2Cl2 H2 (%) (s) (%)
50 90 0 10 0
20 0 30 0 70 14
The total gas pressure in the vessel was kept at approxi¬ mately 0.5 mbar and the vessel temperature was kept at 750 °C during the entire operation.
The above gas composition sequence resulted in the formation of a 1 μm thick Si3N4 film at the substrate surface contain¬ ing less than 0.3% Cl contaminants.
COMPARATIVE EXAMPLE I PA-CVD deposition of a silicon nitride film on a steel sub¬ strate using RF plasma excitation and a constant gas compo¬ sition
This Example was carried out as described in Example II with the exception that a process gas having the following compo¬ sition was continuously fed into the vessel:
NH3 ( % ) S1H2C12 ( % )
90 10
After a period of 60 minutes a 1 μm thick Si3N4 film was de- posited on the substrate surface. According to analysis 0.4% Cl was trapped in the film as a contaminant.
EXAMPLE III
Deposition of a titanium carbide film on a steel substrate using RF plasma excitation.
General reaction scheme: TiCl4 + CH4 -> TiC + 4HC1
The substrate was placed on a holder in the vessel. The ves¬ sel was heated to 500 °C and a gas composed of 70% H2 and 30% Ar was fed into the vessel. A RF electric field (frequency:13.56 MHz, power: 100 W) was applied in order to create a H2/Ar plasma. The H2/Ar plasma was maintained for 60 minutes in order to clean the substrate surface.
Following the preliminary plasma cleaning, the gas composi¬ tion was varied by constantly repeating the following gas composition sequence for a period of 60 minutes:
Feed time H2 (%) CH4 (%) Ar (%) T1C14 (%) (s)
100 75 5 13.5 1.5
100 50 0 50
0
The total gas pressure in the vessel was kept at approxi¬ mately 0.4 mbar and the vessel temperature was kept at 750 °C during the entire operation.
The above gas composition sequence resulted in the formation of a TiC film showing good adherence to the substrate.
COMPARATIVE EXAMPLE II
PA-CVD deposition of a titanium carbide film on a steel sub¬ strate using RF plasma excitation and a constant gas compo¬ sition
This Example was carried out as described in Example III with the exception that a process gas having the following composition was continuously fed into the vessel:
H2 (%) CH4 (%) Ar (%) TiCl4 (%)
75 5 13.5 1.5 After a period of 60 minutes a 1 μm thick TiC film was de¬ posited on the substrate surface. The film showed inferior adherence to the substrate due to chlorine contamination.

Claims

Claims.
1. A plasma assisted chemical vapour deposition (PA-CVD) process for deposition of a solid metal-containing film onto j the surface of a substrate containing at least 50% of Fe or WC, by which the metallic component of the metal-containing film is introduced into the system as a metal halide, c h a r a c t e r i z e d in that it comprises the follow¬ ing steps a) to c):
a) feeding a first process gas essentially composed of: a metal halide, or a metal halide in combination with a diluent gas, a reduc¬ tion agent, a non-metal precursor or any mixture thereof;
b) feeding a second process gas essentially composed of: a metal halide, a diluent gas, a reduction agent, a non- metal precursor or any mixture thereof, the mole fraction of metal halide in this second process gas being substantially lower than the mole fraction of metal halide in the first process gas used in step a);
c) repeating step a) and b) until a metal-containing film of a desired thickness has been formed.
2. A process according to claim 1, c h a r a c t e r i ¬ z e d in that the mole fraction of metal halide in the process gas used in step b) is 0 to 0.5, preferably 0 to 0.1, times the mole fraction of metal halide in the process gas used in step a).
3. A process according to claim 1 or 2, c h a r a c t e ¬ r i z e d in that it comprises the following steps a) to e):
a) feeding a first process gas essentially composed of: a metal halide, or a metal halide in combination with a diluent gas, a reduc¬ tion agent or any mixture thereof;
b) feeding a second process gas essentially composed of: a metal halide, a diluent gas, a reduction agent or any mix¬ ture thereof, the mole fraction of metal halide in this second process gas being substantially lower than the mole fraction of metal halide in the first process gas used in step a);
c) repeating step a) and b) until a metal film of a desired thickness has been formed;
d) feeding a third process gas essentially composed of: a non-metal precursor, or a non-metal precursor in combination with a reduction agent, a diluent gas or any mixture thereof; and
e) repeating step a) to d) until a metal-containing film of a desired thickness has been formed.
4. A process according to claim 3, c h a r a c t e r i - z e d in that the repeating of step a) and b) in step c) is carried out until a metal film having a thickness of 10 to 2000 nm has been formed.
5. A process according to any of the preceding claims, c h a r a c t e r i z e d in that the last step of the process is followed by chemical vapour deposition of a metal-containing film using a continuously fed process gas essentially composed of:
1 to 30 % of a metal halide, 0 to 30 % of a non-metal precursor, 1 to 98 % of a reduction agent, the balance being a diluent gas.
6. A process according to any of the preceding claims, c h a r a c t e r i z e d in that the metal halide contains a metal preferably selected among Al, Si or transition met¬ als, preferably Ti, Cr, W, Mo, V, Hf and Ta.
7. A process according to any of the preceding claims, c h a r a c t e r i z e d in that the reduction agent is a compound capable of reducing the metal halide, preferably selected among H2, CH4, NH3 and CH3CN.
8. A process according to any of the preceding claims, c h a r a c t e r i z e d in that the non-metal precursor is N2, CH4, NH3 or CH3CN.
9. A process according to any of the preceding claims, c h a r a c t e r i z e d in that the diluent gas is a no¬ ble gas, preferably argon.
10. A process according to any of the preceding claims, c h a r a c t e r i z e d in that the substrate essentially consists of hard metal, preferably a WC/Co composit, or steel, preferably HSS (High Speed Steel).
PCT/DK1995/000505 1994-12-16 1995-12-15 A PA-CVD PROCESS FOR DEPOSITION OF A SOLID METAL-CONTAINING FILM ONTO A SUBSTRATE CONTAINING AT LEAST 50 % of Fe or WC WO1996018756A1 (en)

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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001029280A1 (en) * 1999-10-15 2001-04-26 Asm America, Inc. Deposition of transition metal carbides
US6482262B1 (en) 1959-10-10 2002-11-19 Asm Microchemistry Oy Deposition of transition metal carbides
US6599572B2 (en) 2000-01-18 2003-07-29 Asm Microchemistry Oy Process for growing metalloid thin films utilizing boron-containing reducing agents
US6620670B2 (en) 2002-01-18 2003-09-16 Applied Materials, Inc. Process conditions and precursors for atomic layer deposition (ALD) of AL2O3
US6660126B2 (en) 2001-03-02 2003-12-09 Applied Materials, Inc. Lid assembly for a processing system to facilitate sequential deposition techniques
US6734020B2 (en) 2001-03-07 2004-05-11 Applied Materials, Inc. Valve control system for atomic layer deposition chamber
US6765178B2 (en) 2000-12-29 2004-07-20 Applied Materials, Inc. Chamber for uniform substrate heating
US6825447B2 (en) 2000-12-29 2004-11-30 Applied Materials, Inc. Apparatus and method for uniform substrate heating and contaminate collection
US6986914B2 (en) 2001-09-14 2006-01-17 Asm International N.V. Metal nitride deposition by ALD with reduction pulse
US7405143B2 (en) 2004-03-25 2008-07-29 Asm International N.V. Method for fabricating a seed layer
US7780788B2 (en) 2001-10-26 2010-08-24 Applied Materials, Inc. Gas delivery apparatus for atomic layer deposition
US8841182B1 (en) 2013-03-14 2014-09-23 Asm Ip Holding B.V. Silane and borane treatments for titanium carbide films
US8846550B1 (en) 2013-03-14 2014-09-30 Asm Ip Holding B.V. Silane or borane treatment of metal thin films
US8993055B2 (en) 2005-10-27 2015-03-31 Asm International N.V. Enhanced thin film deposition
US9012334B2 (en) 2001-02-02 2015-04-21 Applied Materials, Inc. Formation of a tantalum-nitride layer
US9394609B2 (en) 2014-02-13 2016-07-19 Asm Ip Holding B.V. Atomic layer deposition of aluminum fluoride thin films
US9587310B2 (en) 2001-03-02 2017-03-07 Applied Materials, Inc. Lid assembly for a processing system to facilitate sequential deposition techniques
US9631272B2 (en) 2008-04-16 2017-04-25 Asm America, Inc. Atomic layer deposition of metal carbide films using aluminum hydrocarbon compounds
US9704716B2 (en) 2013-03-13 2017-07-11 Asm Ip Holding B.V. Deposition of smooth metal nitride films
US9786492B2 (en) 2015-11-12 2017-10-10 Asm Ip Holding B.V. Formation of SiOCN thin films
US9786491B2 (en) 2015-11-12 2017-10-10 Asm Ip Holding B.V. Formation of SiOCN thin films
US9941425B2 (en) 2015-10-16 2018-04-10 Asm Ip Holdings B.V. Photoactive devices and materials
US10002936B2 (en) 2014-10-23 2018-06-19 Asm Ip Holding B.V. Titanium aluminum and tantalum aluminum thin films
US10513772B2 (en) 2009-10-20 2019-12-24 Asm International N.V. Process for passivating dielectric films
US10600637B2 (en) 2016-05-06 2020-03-24 Asm Ip Holding B.V. Formation of SiOC thin films
US10643925B2 (en) 2014-04-17 2020-05-05 Asm Ip Holding B.V. Fluorine-containing conductive films
US10847529B2 (en) 2017-04-13 2020-11-24 Asm Ip Holding B.V. Substrate processing method and device manufactured by the same
US10991573B2 (en) 2017-12-04 2021-04-27 Asm Ip Holding B.V. Uniform deposition of SiOC on dielectric and metal surfaces
US11158500B2 (en) 2017-05-05 2021-10-26 Asm Ip Holding B.V. Plasma enhanced deposition processes for controlled formation of oxygen containing thin films

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565676A (en) * 1968-04-01 1971-02-23 Fansteel Metallurgical Corp Chemical vapor deposition method
EP0032887A1 (en) * 1980-01-21 1981-07-29 Sandvik Aktiebolag Method of preparing coated cemented carbide product and resulting product
US4749597A (en) * 1987-10-19 1988-06-07 Spectrum Cvd, Inc. Process for CVD of tungsten
US5279857A (en) * 1991-08-16 1994-01-18 Materials Research Corporation Process for forming low resistivity titanium nitride films

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565676A (en) * 1968-04-01 1971-02-23 Fansteel Metallurgical Corp Chemical vapor deposition method
EP0032887A1 (en) * 1980-01-21 1981-07-29 Sandvik Aktiebolag Method of preparing coated cemented carbide product and resulting product
US4749597A (en) * 1987-10-19 1988-06-07 Spectrum Cvd, Inc. Process for CVD of tungsten
US5279857A (en) * 1991-08-16 1994-01-18 Materials Research Corporation Process for forming low resistivity titanium nitride films

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DIALOG INFORMATION SERVICES, File 351, WORLD PATENT INDEX 81-96, Dialog Accession No. 007546088, WPI Accession No. 88-180020/26, HITACHI LTD. et al., "Glow Discharge Decomposition of Halide to Form Coating on Substrate Using Periodic Introduction of Halide During the Process"; & JP,A,63 118 075 (HITACHI LTD), 23 May *
SURFACE AND COATINGS TECHNOLOGY, Volume 54/55, 1992, KAZUKI KAWATA, "Development of Mass-production-type Plasma Chemical Vapour Deposition Equipment and Its Application to Various Dies", pages 604-608. *

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US7144809B2 (en) 1999-10-15 2006-12-05 Asm International N.V. Production of elemental films using a boron-containing reducing agent
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US11195845B2 (en) 2017-04-13 2021-12-07 Asm Ip Holding B.V. Substrate processing method and device manufactured by the same
US11158500B2 (en) 2017-05-05 2021-10-26 Asm Ip Holding B.V. Plasma enhanced deposition processes for controlled formation of oxygen containing thin films
US11776807B2 (en) 2017-05-05 2023-10-03 ASM IP Holding, B.V. Plasma enhanced deposition processes for controlled formation of oxygen containing thin films
US10991573B2 (en) 2017-12-04 2021-04-27 Asm Ip Holding B.V. Uniform deposition of SiOC on dielectric and metal surfaces

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