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WO1996018756A1 - TECHNIQUE DE DEPOSITION EN PHASE VAPEUR PAR PROCEDE CHIMIQUE ASSISTEE PAR PLASMA, POUR LE DEPOT D'UN FILM CONTENANT UN METAL SOLIDE SUR UN SUBSTRAT CONTENANT AU MOINS 50 % DE Fe OU DE WC - Google Patents

TECHNIQUE DE DEPOSITION EN PHASE VAPEUR PAR PROCEDE CHIMIQUE ASSISTEE PAR PLASMA, POUR LE DEPOT D'UN FILM CONTENANT UN METAL SOLIDE SUR UN SUBSTRAT CONTENANT AU MOINS 50 % DE Fe OU DE 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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English (en)
Inventor
Kristian GLEJBØL
Nini Hamawi Pryds
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NKT Research Center AS
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NKT Research Center AS
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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
    • C23C16/44—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:

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  • 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

Cette invention se rapporte à une nouvelle technique de dépositioe en phase vapeur par procédé chimique assistée par plasma, qui sert à déposer un film contenant un métal solide sur la surface d'un substrat renfermant au moins 50 % de Fe ou de WC (tel qu'un métal dur ou de l'acier), le constituant métallique du film contenant le métal étant introduit dans le système sous la forme d'un halogénure de métal. Cette nouvelle technique consiste à faire passer la composition du gaz de traitement entre une haute teneur en halogènure métallique et une basse teneur en halogénure métallique, pour que le film déposé adhère mieux au substrat.
PCT/DK1995/000505 1994-12-16 1995-12-15 TECHNIQUE DE DEPOSITION EN PHASE VAPEUR PAR PROCEDE CHIMIQUE ASSISTEE PAR PLASMA, POUR LE DEPOT D'UN FILM CONTENANT UN METAL SOLIDE SUR UN SUBSTRAT CONTENANT AU MOINS 50 % DE Fe OU DE WC Ceased WO1996018756A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DK143694 1994-12-16
DK1436/94 1994-12-16

Publications (1)

Publication Number Publication Date
WO1996018756A1 true WO1996018756A1 (fr) 1996-06-20

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PCT/DK1995/000505 Ceased WO1996018756A1 (fr) 1994-12-16 1995-12-15 TECHNIQUE DE DEPOSITION EN PHASE VAPEUR PAR PROCEDE CHIMIQUE ASSISTEE PAR PLASMA, POUR LE DEPOT D'UN FILM CONTENANT UN METAL SOLIDE SUR UN SUBSTRAT CONTENANT AU MOINS 50 % DE Fe OU DE WC

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US6620670B2 (en) 2002-01-18 2003-09-16 Applied Materials, Inc. Process conditions and precursors for atomic layer deposition (ALD) of AL2O3
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US7208413B2 (en) 2000-06-27 2007-04-24 Applied Materials, Inc. Formation of boride barrier layers using chemisorption techniques
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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
US9394609B2 (en) 2014-02-13 2016-07-19 Asm Ip Holding B.V. Atomic layer deposition of aluminum fluoride thin films
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