WO2009086263A1 - Procédés pour préparer des films minces utilisant des précurseurs de pyrrolyl-métal substitués - Google Patents

Procédés pour préparer des films minces utilisant des précurseurs de pyrrolyl-métal substitués Download PDF

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Publication number
WO2009086263A1
WO2009086263A1 PCT/US2008/087938 US2008087938W WO2009086263A1 WO 2009086263 A1 WO2009086263 A1 WO 2009086263A1 US 2008087938 W US2008087938 W US 2008087938W WO 2009086263 A1 WO2009086263 A1 WO 2009086263A1
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titanium
precursor
adduct
formula
substrate
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PCT/US2008/087938
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English (en)
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Peter Nicholas Heys
Hywel Owen Davies
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Sigma-Aldrich Co.
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Publication of WO2009086263A1 publication Critical patent/WO2009086263A1/fr

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/409Oxides of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • C23C16/45553Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD

Definitions

  • the present invention relates to methods of preparing thin films by atomic layer deposition (ALD) using substituted pyrrolyl-metal precursors.
  • ALD atomic layer deposition
  • ALD is a known method for the deposition of thin films. It is a self- limiting, sequential unique film growth technique based on surface reactions that can provide atomic layer control and deposit conformal thin films of materials provided by precursors onto substrates of varying compositions.
  • the precursors are separated during the reaction. The first precursor is passed over the substrate producing a monolayer on the substrate. Any excess unreacted precursor is pumped out of the reaction chamber. A second precursor is then passed over the substrate and reacts with the first precursor, forming a monolayer of film on the substrate surface. This cycle is repeated to create a film of desired thickness.
  • ALD processes have applications in nanotechnology and fabrication of semiconductor devices such as capacitor electrodes, gate electrodes, adhesive diffusion barriers and integrated circuits. Further, dielectric thin films having high dielectric constants (permittivities) are necessary in many sub-areas of microelectronics and optelectronics. The continual decrease in the size of microelectronics components has increased the need for the use of such dielectric films.
  • the methods comprise delivering at least one precursor, or an adduct thereof, to a substrate, wherein the at least one precursor corresponds in structure to Formula I:
  • M is Sr, Ba or Ca
  • R is independently Q-Cio-alkyl or Q-Cio-alkoxy; and n is 1, 2, 3 or 4.
  • Figure 1 is a representation of the X-ray structure of bis(2,5-di-tert- butylpyrrolyl)barium(THF)2.
  • Figure 2 is a graphical representation of thermogravimetric analysis (TGA) data demonstrating % weight loss vs. temperature of bis(2,5-di-tert- butylpyrrolyl) strontium derived from its THF adduct.
  • TGA thermogravimetric analysis
  • a dielectric thin film as used herein refers to a thin film having a high permittivity.
  • precursor refers to an organometallic molecule, complex and/or compound which is delivered to a substrate for deposition to form a thin film by ALD.
  • the precursor may be dissolved in an appropriate hydrocarbon or amine solvent.
  • hydrocarbon solvents include, but are not limited to aliphatic hydrocarbons, such as hexane, heptane and nonane; aromatic hydrocarbons, such as toluene and xylene; aliphatic and cyclic ethers, such as diglyme, triglyme and tetraglyme.
  • appropriate amine solvents include, without limitation, octylamine and N,N-dimethyldodecylamine.
  • the precursor may be dissolved in toluene to yield a 0.05 to IM solution.
  • the term "adduct” refers to a product formed from an addition reaction between at least (1) a precursor corresponding to Formula I and (2) an appropriate solvent, such as a Lewis base.
  • a Lewis base as used herein, is any molecule with an electron lone pair in a bonding orbital (also known as an electron donating group).
  • An example of such Lewis base is tetrahydrofuran (THF).
  • pyr* refers to a pyrrolyl ligand which is bound to a metal center. All four carbon atoms and the nitrogen atom of the pyrrole ligand can be bound to the metal center in ⁇ 5 -coordination by ⁇ bonding. Alternatively, only the nitrogen atom may be bonded to the metal center by ⁇ bonding resulting in incoordination. Other types of coordination bonding may be possible as well.
  • alkyl (alone or in combination with another term(s)) refers to a saturated hydrocarbon chain of 1 to about 10 carbon atoms in length, such as, but not limited to, methyl, ethyl, propyl and butyl.
  • the alkyl group may be straight-chain or branched-chain.
  • propyl encompasses both w-propyl and iso- propyl; butyl encompasses w-butyl, sec-butyl, zso-butyl and tert-butyl.
  • Me refers to methyl
  • Et refers to ethyl.
  • alkoxy refers to an alkylether substituent, i.e., -O-alkyl.
  • alkylether substituent i.e., -O-alkyl.
  • substituents include methoxy (- O-CH 3 ), ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, and tert- butoxy.
  • a method of preparing a metal oxide thin film by atomic layer deposition comprises delivering at least one precursor, or an adduct thereof, to a substrate, wherein the at least one precursor corresponds in structure to Formula I:
  • M is Sr, Ba or Ca
  • R is independently Ci-Cio-alkyl or Q-Qo-alkoxy; and n is 1, 2, 3 or 4.
  • the at least one precursor according to Formula I or an adduct of the at least one precursor according to Formula I is deposited onto a substrate to form a thin film by ALD.
  • Lewis base solvents which may be used to form an adduct of a precursor according to Formula I include, without limitation, ethers and amines.
  • ethers corresponding to the Formula II: R 2 O and cyclic ethers, such as THF may be used.
  • amines corresponding to the Formula III: R 3 N may also be used.
  • R is Q-Qo-alkyl.
  • the solvent utilized to form an adduct of a precursor according to Formula I is THF.
  • the metal center of the at least one precursor according to Formula I is comprised of an alkaline earth metal, such as barium, strontium and/or calcium.
  • the at least one precursor corresponds to Formula I, wherein R is butyl such as w-butyl, sec-butyl, iso-buty ⁇ and tert-butyl. In a particular embodiment, butyl is tert-butyl.
  • the at least one precursor corresponds to Formula I, wherein R is propyl such as w-propyl and iso-propyl.
  • R is propyl such as w-propyl and iso-propyl.
  • propyl is iso-propyl.
  • the at least one precursor corresponds to Formula I wherein:
  • M is Sr or Ba
  • R is Q-Cio-alkyl; and n is 1, 2 or 3.
  • the at least one precursor corresponds to Formula I wherein: M is Sr;
  • R is methyl, ethyl, propyl or butyl; and n is 2 or 3.
  • the at least one precursor corresponds to Formula I wherein:
  • M is Ba
  • R is methyl, ethyl, propyl or butyl; and n is 2 or 3.
  • the at least one precursor corresponds to Formula I wherein:
  • M is Ca
  • R is methyl, ethyl, propyl or butyl; and n is 2 or 3.
  • an adduct of the at least one precursor corresponding to Formula I is: [0031] The adduct is formed by THF bonding to the metal center through its oxygen atom as a donor/adduct bond.
  • the method further comprises delivering for deposition at least one volatile titanium precursor and a reactive oxygen species to form a mixed metal oxide thin film, such as BaTiO 3 , SrTiO 3 or CaTiO 3 .
  • a mixed metal oxide thin film such as BaTiO 3 , SrTiO 3 or CaTiO 3 .
  • the precursors corresponding to Formula I, or adducts thereof, can also be exploited in ALD of other oxide thin films containing barium, strontium and/or calcium.
  • Examples of volatile titanium precursors include, without limitation, titanium halide, titanium alkoxide, titanium nitrate, an alkylamino complex of titanium, a cyclopentadienyl complex of titanium, a silylamido complex of titanium, a silylamido complex of titanium, titanium dialkyldithiocarbamate and a titanium- ⁇ -diketonate.
  • two or more precursors according to Formula I can be used to form a mixed metal oxide film.
  • the precursors corresponding to Formula I, or adducts thereof, can be deposited onto the substrate in pulses alternating with pulses of an oxygen source, such as a reactive oxygen species.
  • oxygen source such as a reactive oxygen species.
  • oxygen source include, without limitation, H 2 O, O 2 and/or ozone.
  • the film can also be formed by the at least one precursor corresponding to Formula I, or adduct thereof, independently or in combination with a co-reactant.
  • co-reactants include, but are not limited to hydrogen, hydrogen plasma, oxygen, air, water, H 2 O 2 , ammonia, hydrazines, allylhydrazines, boranes, silanes, ozone or any combination thereof.
  • substrates can be used in the methods of the present invention.
  • the precursors according to Formula I, or adducts thereof may be delivered for deposition on substrates such as, but not limited to, silicon, silicon oxide, silicon nitride, tantalum, tantalum nitride, or copper.
  • the ALD methods of the invention encompass various types of ALD processes.
  • conventional ALD is used to form a metal oxide film of the invention.
  • conventional and/or pulsed injection ALD process see for example, George S. M., et. al. J. Phys. Chem. 1996. 100:13121-13131.
  • liquid injection ALD is used to form a ruthenium- containing film, wherein a liquid precursor is delivered to the reaction chamber by direct liquid injection as opposed to vapor draw by a bubbler.
  • liquid injection ALD process see, for example, Potter R. J., et. al. Chem. Vap. Deposition. 2005. 11(3): 159.
  • Examples of liquid injection ALD growth conditions include, but are not limited to:
  • Pulse sequence (sec.) (precursor/purge/HiO/purge): will vary according to chamber size. Number of cycles: will vary according to desired film thickness.
  • photo-assisted ALD is used to form a ruthenium- containing film.
  • photo-assisted ALD processes see, for example, U.S. Patent No. 4,581,249.
  • the organometallic precursors according to Formula I, or adducts thereof, utilized in these methods may be liquid, solid, or gaseous.
  • the precursors or adducts thereof are liquid at ambient temperatures with high vapor pressure for consistent transport of the vapor to the process chamber.
  • the method of the invention is utilized for applications such as dynamic random access memory (DRAM) and complementary metal oxide semi-conductor (CMOS) for memory and logic applications, such as on silicon chips.
  • DRAM dynamic random access memory
  • CMOS complementary metal oxide semi-conductor
  • ALD relies substantially on chemical reactivity and not thermal decomposition. Therefore, there are fundamental differences in the characteristics desirable for a suitable precursor (or adduct thereof).
  • the precursor must be thermally stable at the temperatures employed and should be sufficiently volatile to allow deposition onto the substrate or sufficiently soluble in a desired solvent if the process of d.l.i. (direct liquid injection) is to be used.
  • a fast and complete chemical reaction is necessary between the metal precursor and the oxide source. However, the reaction should only take place at the substrate surface so as not to damage the underlying structure, and by-products, such as carbon and nitrogen species, should be removed readily from the surface.
  • a substituted pyrrolyl ligand metal complex demonstrates useful and improved properties for ALD processes, such as a high permittivity.
  • Compounds comprising substituted pyrrolyl metal complexes have never been considered for oxide growth applications.
  • the precursors corresponding to Formula I, or adducts thereof, provide an increased ability to deposit metal oxide films by ALD.
  • the reaction mixture was stirred for ⁇ 30 min at ⁇ -75 0 C and then allowed to warm up to room temperature.
  • the reaction mixture was cooled to ⁇ -5 0 C and HCl (1.0 M aqueous, 3.5 L, 3.5 mol) was added dropwise.
  • Methyl t-butyl ether (3.5 L) was added then and the reaction mixture was stirred for 40 min.
  • the organic was separated and the aqueous layer was extracted with methyl t-butyl ether (3.5 L).
  • the organic layer was separated and the combined organic extracts were washed with brine (3.5 L X 2).
  • Reaction mixture was refluxed for 3.5 h. GC showed 77% conversion. Reaction mixture was allowed to cool down to room temperature, then diluted with methyl t-butyl ether (10 mL) and quenched slowly with water (10.0 mL). Organic layer was diluted with MTBE
  • the sodium or potassium salt of bis(2,5-di-tert-butylpyrrolyl) is reacted with strontium diiodide, barium diiodide or calcum diiodide in THF to yield mono-THF adducts of either bis(2,5-di-tert-butylpyrrolyl)strontium, bis(2,5-di-tert- butylpyrrolyl)barium or bis(2,5-di-tert-butylpyrrolyl)calcium. See Schumann H., et al.
  • NMR spectra of these compounds is exemplified by that of bis(2,5-di- tert-butylpyrrolyl) strontium, derived from its THF adduct compound by heating at 120 0 C under vacuum (0.1 Torr) for 2 hours in a cold finger sublimation apparatus. Adduct free compound was obtained by sublimation starting at 200-240 0 C.
  • Figure 1 illustrates, as an example of these compounds, the X-ray structure of bis(2,5-di-tert-butylpyrrolyl)barium(THF) 2 .
  • the results indicate that, whereas the structures of both the calcium and strontium analogues show only one coordinated THF molecule, the barium analogue has two coordinated THF molecules, presumably due to its larger size.
  • Strontium titanium oxide thin films are deposited in a custom-built ALD reactor.
  • Bis(2,5-di-tert-butylpyrrolyl)Sr(THF), titanium tetraisopropoxide (Ti(O 1 C 3 Hv) 4 ) and ozone are used as precursors.
  • the strontium titanium oxide films are deposited on silicon wafer substrates. Prior to deposition, the wafer substrates are prepared by dicing the wafer (linch x 1 A inch), and 1% HF polished.
  • the growth temperature is about 300 0 C.
  • the growth pressure is about 250 milliTorr.
  • the reactor is continuously purged with 30 seem of dry nitrogen.
  • the growth of SrTiO 3 is implemented by using alternate Ti-O and Sr-O deposition cycles.
  • the Ti-O cycle is made up of four steps: (i) pulse of Ti(O 1 C 3 Hv) 4 , (ii) purge with inert nitrogen gas, (iii) pulse of ozone, and (iv) purge with nitrogen gas.
  • the Sr-O cycle is made up of four steps: (i) pulse of bis(2,5-di-tert- butylpyrrolyl)Sr(THF), (ii) purge with nitrogen gas, (iii) pulse of H 2 O, and (iv) purge with nitrogen gas.
  • the composition of the film is controlled by the ratio of the Ti-O and Sr-O cycles.
  • the alternation of the Ti-O and Sr-O cycles is implemented so that there are at maximum two similar cycles in succession.
  • q determines the thickness of the film.
  • the total amount of cycles is typically 300.

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne des procédés de préparation de films minces en oxyde de métal par dépôt de couche atomique. Un procédé comprend la délivrance d'au moins un précurseur, ou d'un produit d'additionnel de celui-ci, à un substrat, le au moins un précurseur correspondant en structure à la formule I : M[(R)npyr*]2 (Formule I) dans laquelle : M est Sr, Ba ou Ca; R est indépendamment un alkyle en C1 à C10 ou alcoxy en C1 à C10; et n vaut 1, 2, 3 ou 4.
PCT/US2008/087938 2007-12-28 2008-12-22 Procédés pour préparer des films minces utilisant des précurseurs de pyrrolyl-métal substitués WO2009086263A1 (fr)

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Cited By (15)

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EP2256121A1 (fr) 2009-05-29 2010-12-01 Air Products and Chemicals, Inc. Précurseurs de métal volatile de groupe 2
EP2371821A1 (fr) 2010-02-05 2011-10-05 Air Products and Chemicals, Inc. Imidazoles volatils et précurseurs métalliques du groupe 2 de type imidazole
WO2011156699A1 (fr) 2010-06-11 2011-12-15 Air Products And Chemicals, Inc. Complexes de ligands imidazoles
US8476467B2 (en) 2007-07-24 2013-07-02 Sigma-Aldrich Co. Llc Organometallic precursors for use in chemical phase deposition processes
US8481121B2 (en) 2007-07-24 2013-07-09 Sigma-Aldrich Co., Llc Methods of forming thin metal-containing films by chemical phase deposition
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US8613975B2 (en) 2008-05-23 2013-12-24 Sigma-Aldrich Co. Llc Methods of producing high-K dielectric films using cerium-based precursors
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US8859045B2 (en) 2012-07-23 2014-10-14 Applied Materials, Inc. Method for producing nickel-containing films
US8927748B2 (en) 2011-08-12 2015-01-06 Sigma-Aldrich Co. Llc Alkyl-substituted allyl carbonyl metal complexes and use thereof for preparing dielectric thin films
US9028917B2 (en) 2009-08-07 2015-05-12 Sigma-Aldrich Co. Llc High molecular weight alkyl-allyl cobalttricarbonyl complexes and use thereof for preparing dielectric thin films
US9194040B2 (en) 2012-07-25 2015-11-24 Applied Materials, Inc. Methods for producing nickel-containing films
US11047046B2 (en) 2017-01-26 2021-06-29 Asm Ip Holding B.V. Vapor deposition of thin films comprising gold
US11976352B2 (en) 2018-02-12 2024-05-07 Merck Patent Gmbh Methods of vapor deposition of ruthenium using an oxygen-free co-reactant

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US8568530B2 (en) 2005-11-16 2013-10-29 Sigma-Aldrich Co. Llc Use of cyclopentadienyl type hafnium and zirconium precursors in atomic layer deposition
US8476467B2 (en) 2007-07-24 2013-07-02 Sigma-Aldrich Co. Llc Organometallic precursors for use in chemical phase deposition processes
US8481121B2 (en) 2007-07-24 2013-07-09 Sigma-Aldrich Co., Llc Methods of forming thin metal-containing films by chemical phase deposition
US8613975B2 (en) 2008-05-23 2013-12-24 Sigma-Aldrich Co. Llc Methods of producing high-K dielectric films using cerium-based precursors
EP2540731A1 (fr) 2009-05-29 2013-01-02 Air Products and Chemicals, Inc. Précurseurs de métal volatile de groupe 2
US20110120875A1 (en) * 2009-05-29 2011-05-26 Air Products And Chemicals, Inc. Volatile Group 2 Metal Precursors
JP2011001362A (ja) * 2009-05-29 2011-01-06 Air Products & Chemicals Inc 揮発性第二族金属前駆体
US8859785B2 (en) 2009-05-29 2014-10-14 Air Products And Chemicals, Inc. Volatile group 2 metal precursors
EP2256121A1 (fr) 2009-05-29 2010-12-01 Air Products and Chemicals, Inc. Précurseurs de métal volatile de groupe 2
JP2014055175A (ja) * 2009-05-29 2014-03-27 Air Products And Chemicals Inc 揮発性第二族金属前駆体
US9028917B2 (en) 2009-08-07 2015-05-12 Sigma-Aldrich Co. Llc High molecular weight alkyl-allyl cobalttricarbonyl complexes and use thereof for preparing dielectric thin films
JP2012062303A (ja) * 2010-02-05 2012-03-29 Air Products & Chemicals Inc 揮発性イミダゾール及び二族イミダゾール系金属前駆体
US8703103B2 (en) 2010-02-05 2014-04-22 Air Products And Chemicals, Inc. Volatile imidazoles and group 2 imidazole based metal precursors
EP2371821A1 (fr) 2010-02-05 2011-10-05 Air Products and Chemicals, Inc. Imidazoles volatils et précurseurs métalliques du groupe 2 de type imidazole
US8680289B2 (en) 2010-06-11 2014-03-25 Air Products And Chemicals, Inc. Complexes of imidazole ligands
US9018387B2 (en) 2010-06-11 2015-04-28 Air Products And Chemicals, Inc. Complexes of imidazole ligands
WO2011156699A1 (fr) 2010-06-11 2011-12-15 Air Products And Chemicals, Inc. Complexes de ligands imidazoles
US8691710B2 (en) 2011-02-08 2014-04-08 Air Products And Chemicals, Inc. Group IV metal complexes for metal-containing film deposition
US8927748B2 (en) 2011-08-12 2015-01-06 Sigma-Aldrich Co. Llc Alkyl-substituted allyl carbonyl metal complexes and use thereof for preparing dielectric thin films
WO2014004949A1 (fr) * 2012-06-29 2014-01-03 Applied Materials, Inc. Dépôt de films contenant des métaux alcalino-terreux
US10233541B2 (en) 2012-06-29 2019-03-19 Applied Materials, Inc. Deposition of films containing alkaline earth metals
US8859045B2 (en) 2012-07-23 2014-10-14 Applied Materials, Inc. Method for producing nickel-containing films
US9194040B2 (en) 2012-07-25 2015-11-24 Applied Materials, Inc. Methods for producing nickel-containing films
US11047046B2 (en) 2017-01-26 2021-06-29 Asm Ip Holding B.V. Vapor deposition of thin films comprising gold
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