WO1992015112A1 - Methods and apparatus for material deposition - Google Patents

Methods and apparatus for material deposition Download PDF

Info

Publication number
WO1992015112A1
WO1992015112A1 PCT/US1992/001380 US9201380W WO9215112A1 WO 1992015112 A1 WO1992015112 A1 WO 1992015112A1 US 9201380 W US9201380 W US 9201380W WO 9215112 A1 WO9215112 A1 WO 9215112A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
mist
deposition chamber
peripheral portion
solution
Prior art date
Application number
PCT/US1992/001380
Other languages
French (fr)
Inventor
Carlos A. Paz De Araujo
Larry D. Mcmillan
Tom L. Roberts
Original Assignee
Symetrix Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Symetrix Corporation filed Critical Symetrix Corporation
Priority to KR1019930702549A priority Critical patent/KR100202532B1/en
Priority to JP4511586A priority patent/JP2860505B2/en
Publication of WO1992015112A1 publication Critical patent/WO1992015112A1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0493—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases using vacuum
    • 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
    • C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4486—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by producing an aerosol and subsequent evaporation of the droplets or particles
    • 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
    • C23C16/45563—Gas nozzles
    • C23C16/4558—Perforated rings
    • 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
    • C23C16/46—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 heating the substrate
    • 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
    • C23C16/48—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 by irradiation, e.g. photolysis, radiolysis, particle radiation
    • C23C16/482—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 by irradiation, e.g. photolysis, radiolysis, particle radiation using incoherent light, UV to IR, e.g. lamps
    • 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
    • C23C16/52—Controlling or regulating the coating process
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/68—Crystals with laminate structure, e.g. "superlattices"
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H01L28/55—Capacitors with a dielectric comprising a perovskite structure material
    • H01L28/56—Capacitors with a dielectric comprising a perovskite structure material the dielectric comprising two or more layers, e.g. comprising buffer layers, seed layers, gradient layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H10N30/076—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by vapour phase deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H01L28/55—Capacitors with a dielectric comprising a perovskite structure material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam

Definitions

  • the invention relates to methods for depositing high quality films of complex (compound) materials on substrates at high deposition rates, and apparatus for effecting such methods.
  • the invention relates to nonreactive chemical vapor deposition (CVD) methods and apparatus for depositing high quality, stoichiometrically-correct, thin films of a large variety of complex compounds at high deposition rates utilizing stabilized liquid compound sources.
  • CVD nonreactive chemical vapor deposition
  • the present invention has been developed to overcome the many problems and disadvantages associated with known deposition techniques for depositing thin films of complex chemical compounds including those discussed above, and to generally fulfill a great need in the art by providing a production worthy process which can be used for easily and economically producing thin films (from a few angstroms to microns in thickness) of various complex materials such as ferroelectrics, superconductors, and metal oxides.
  • Fig. 1 is a schematic view of a CVD apparatus according to a first embodiment of the invention.
  • Fig. 2 is an enlarged plan view of a nozzle assembly and an exhaust assembly used in the embodiment of Fig. 1.
  • Fig.3 is an enlarged schematic view of a manifold system used in the first and second embodiments of the invention.
  • Fig. 4 is a vertical cross sectional view of a preferred apparatus for forming a mist of a stabilized solution according to the present invention.
  • Figs. 5a and 5b show modifications of the apparatus of Fig. 4.
  • Fig. 6 is a schematic flow chart showing the preparation of a stabilized solution to be used in forming a thin film of lead zirconium titanate according to the present invention.
  • stabilized sources or stabilized solutions of desired chemical compounds will initially be prepared and then mists or vapors of the solutions will be generated, flowed into a deposition chamber and deposited in thin films/layers on substrates disposed within the deposition chamber.
  • Such stabilized solutions include at least all of those used in known liquid application techniques and specifically include sol-gels (which include alcohols as the solvent base thereof), metallorganic decomposition (MOD) formulations (which utilize n-decanoic acid as the solvent base thereof), solutions having water as the solvent base thereof, solutions having carboxylic acid as the solvent base thereof, etc.
  • the term "stabilized source” as used herein is intended to designate a source which is obtained by mixing precursors for each element using sol-gel techniques, or other wet chemistry mixing techniques, which lead to a common solvent, and then using the solution having that common solvent as the sole source for the entire compound. Other sources may also be used in parallel for doping or modifying the compound. In the stabilized source the elements are already in the compound in solution with the common solvent or metallorganic precursor.
  • the stabilized solutions used in the present invention are substantially less toxic and easier to handle than the corresponding reactants which are used in conventional, reactive CVD methods as discussed above, whereby the stabilized solutions can be handled and processed at substantially lower cost than the corresponding reactants.
  • the stabilized compound sources assures high quality of the thin films produced thereby because the stabilized source can be accurately and consistently produced such that the desired chemical compound contained therein is uniformly, stoichiometricalh/ correct, and because the deposition methods of the present invention do not involve any chemical reactions which might destabilize the chemical compound of its predetermined molecular formulation. Instead, thin films of the stabilized source are directly deposited on substrates from a mist/vapor under vacuum at ambient temperatures and subsequently dried.
  • Fig. 1 there is shown a thin film deposition apparatus according to a preferred embodiment of the invention, the apparatus being generally designated at 1.
  • the apparatus 1 generally comprises a vacuum chamber 2, a substrate holder 4, a barrier plate 6, a nozzle assembly 8, and an exhaust assembly 10.
  • the vacuum chamber 2 includes a main body 12, a lid 14 which is securable over the main body to define an enclosed space within the vacuum chamber, and the chamber is connected to an appropriate vacuum source (not shown) as generally indicated at 16.
  • the lid 14 is preferably pivotally connected to the main body 12 using a hinge as indicated at 18.
  • the substrate holder 4 is preferably supported on a rotatable shaft 20 which is in turn connected to a motor (not shown) so that the holder may, if desired, be rotated during a deposition process.
  • Indicated at 22 is an insulating connector which electrically insulates the substrate holder 4 and a substrate 5 supported thereon from the rest of the deposition apparatus 1 so that a DC or AC (RF) bias can be created between the substrate holder 4 and the barrier plate 6, if desired, utilizing the DC/RF feedthrough indicated at 23.
  • RF AC
  • Such a DC bias could be utilized, for example, for field-poling of thin films as they are being deposited on the substrate 5.
  • an electrical source (not shown) would be operativery connected across the barrier 6 and the substrate holder 4.
  • the barrier plate 6 is preferably made of an electrically conductive material such as stainless steel, and is of sufficiently large size to extend completely over the substrate 5 in parallel thereto so that a vaporized source or mist as injected by the nozzle assembly 8 is forced to flow between the plate 6 and the substrate holder 4 over the substrate 5.
  • the barrier plate 6 is preferably connected to the lid 14 by a shaft 24 so that the plate 6 will be moved away from the substrate 5 whenever the lid is opened.
  • the shaft 24 is preferably adjustable in length so that the spacing between the holder 4 and the plate 6 can be adjusted depending on the source materials, the flow rate, etc. For example, the spacing may be adjustable to define a spacing in the range of 2 - 50 mm.
  • the nozzle assembly 8 preferably includes an input tube 26 which receives a vaporized source from a manifold assembly 40 as discussed below in relation to Fig. 3, and an arcuate nozzle tube 28 having a plurality of small holes with removable screws 30 provided in a uniformly spaced manner along a surface of the tube 28 facing inwardly of the deposition chamber 2.
  • the screws 30 can be selectively removed depending on the stabilized source, flow rate, etc. to adjust the flow of the vaporized source over the substrate 5.
  • Indicated at 32 are end caps of the tube 28.
  • the structure of the exhaust assembly 10 is substantially the same as that of the nozzle assembly 8, except that a pipe 34 leads to a vacuum/exhaust source (not shown).
  • the arcuate tube 28 of the nozzle assembly 8 and the corresponding arcuate tube of the exhaust assembly 10 will preferably surround respective, oppositely disposed peripheral portions of the substrate 5, and the arcuate tubes will be spaced from each other across a central or intermediate portion of the substrate 5.
  • the substrate holder 4, the barrier plate 6, the nozzle assembly 8 and the exhaust assembly 5 collectively cooperate to define a relatively small deposition cavity surrounding an upper/exposed surface of the substrate 5, and within which the vaporized source is substantially contained throughout the deposition process.
  • the manifold assembly 40 is utilized for supplying a vaporized source to the nozzle assembly 8, and generally comprises a mixing chamber 42, a plurality of inlets 44 which are connected to corresponding source generators 46 through respective valves 48, a valve 50 for regulating flow from the mixing chamber 42 to the nozzle assembly 8, and an exhaust valve 52.
  • one or more of the source generators 46 are utilized to generate one or more different vaporized sources or mists which are then flowed into the mixing chamber 42 through the valves -48 and inlets 44.
  • the vaporized sources as flowed into the mixing chamber 42 are mixed to form a single, uniform vaporized source or mist, which is then flowed into the vacuum chamber 2 at an appropriate flow rate through the valve 50.
  • the valve 50 can be selectively closed off so that the vacuum chamber 2 can be pumped down to dry a deposited film of a stabilized liquid source, or to clean and purge the system when necessary.
  • the outlet of the exhaust valve 52 is connected to a vacuum source (not shown) so that, when necessary to exhaust purge one or more of the mist generators 46, the valve 50 can be closed off, the valve 52 and one or more of the valves -48 can be opened, and the mixing chamber 42 can be pumped down to clean and purge the source generators) and the mixing chamber.
  • a mist will be flowed from the manifold assembly 40 into the nozzle assembly 8 at ambient temperature or slightly above room temperature.
  • the generator 46 includes a closed container 54, an ultrasonic transducer 56 fluid-tightly sealed into the bottom of the container 54, a valve 58 for introducing a stabilized liquid source such as a sol-gel or an MOD formulation into the container 54 while the container is maintained under sealed, vacuum-tight conditions, and an inlet port 60 and an outlet port 62 for passing a carrier gas through the container 54.
  • a stabilized liquid source such as a sol-gel or an MOD formulation
  • a stabilized liquid source 64 will be introduced into the container 54 through the valve 58 up to an appropriate level as measured by a level-detecting means (not shown), the transducer 56 is activated to generate a mist 66 of the stabilized liquid source, and an appropriate carrier gas is passed through the mist 66 via the ports 60, 62 where it becomes wet or saturated with the mist, and the wet carrier gas is then passed from the outlet port 62 into the manifold assembly -40 as discussed above.
  • the carrier gas will normally, be an inert gas such as argon or helium, but may comprise a reactive gas in appropriate situations.
  • the valve 58 will be selectively actuated as necessary to maintain the stabilized liquid source 64 at an appropriate level within the container 54.
  • the preferred source generator -46 as shown in Fig. 4 is particularly advantageous because it creates a vaporized source which can be effectively flowed or injected into the vacuum deposition chamber 2 without complications such as freezing.
  • Fig. 5a there is shown a source generator -46' which is modification of the source generator 46 shown in Fig. 4 whereby the ultrasonic transducer 56 does not come into contact with the stabilized liquid source 64.
  • the stabilized liquid source 64 is contained within a first, closed container 54' while the transducer 56 is sealingly fitted to a bottom wall of a second, open container 68, a working medium 70 such as water or another liquid is disposed in the second container 68 over the transducer, and the first container 54' is disposed in spaced relation above an upper surface of the working medium 70 such that a mist plume 72 of the working medium created by the ultrasonic transducer contacts a bottom wall of the first container 54' for thereby creating the mist 66 of the stabilized liquid 64 within the first container 54', which is then flowed into the manifold assembly 40 in the same manner as discussed above in relation to Fig. 4.
  • the modified source generator -46' shown in Fig. 5 has all of the advantages of the source generator 46 shown in Fig. 4, as well as an additional advantage that the ultrasonic transducer 56 does not become contaminated with a stabilized liquid used to form a desired thin film.
  • FIG. 5b there is shown another modification of the mist generating apparatus of Fig.4.
  • the modification of Fig.5b is very similar to that of Fig. 4 except that the transducer 56 is suspended in the generator 46" above the stabilized liquid source rather than being sealed into the bottom wall of the container.
  • a stabilized liquid source could be provided within a closed container and an appropriate carrier gas could be simply bubbled through the stabilized liquid and then flowed into the mixing chamber 40; or a spray nozzle could be used to generate a mist of a stabilized liquid source within a closed container, and an appropriate carrier gas could be flowed through the mist and into the mixing chamber 40 using an inlet and outlet port similar to the ports 60, 62 shown in Fig. 4.
  • YMn0 3 An example of the sol-gel synthesis of YMn0 3 follows. 1 gm. of yttrium isopropoxide Y[OCH(CH 3 ) 2 ] 3 was mixed with 8 ml. of 2-methoxyethanol. The yttrium isopropoxide did not go into solution, but was forced into solution by the addition of approximately 25 drops (slightly over one ml.) of hydrochloric acid. 0.25 grams of manganese acetate Mn(OOCCH 3 ) 2 -H 2 0 was mixed with 5 ml. 2-meth ⁇ xyethanol. The manganese acetate would not dissolve in the 2- meth ⁇ xyethanol, but was forced into solution by the addition of approximately 10 drops of hydrochloric acid.
  • the yttrium and manganese solutions were then mixed together at room temperature resulting in a slightly yellow colored solution.
  • the resulting YMn0 3 solution did not form a film when spun onto a silicon wafer.
  • Adding H 2 0 for hydrolysis did not improve the film-forming characteristics.
  • the addition of approximately 25 drops of titanium isopropoxide (a gel former) to the yttrium manganese solution resulted in a solution which remained clear for approximately 3 hours and formed good films when spun onto a silicon wafer.
  • Fig. 6 there is shown an exemplary flow chart depicting the preparation of a stabilized liquid solution of lead zirconium titanate (PZT hereinafter) to be deposited utilizing the apparatus of Figs. 1-5.
  • PZT lead zirconium titanate
  • steps P« -P 3 stabilized liquid precursors of titanium isopropoxide, zirconium N-propoxide and lead acetate are respectively formed utilizing 2-methoxyethanol as the common solvent of each of the precursors.
  • step P 4 the stabilized solutions of titanium isopropoxide and zirconium n-propoxide are mixed, while at step P 5 such mixture is further mixed with the stabilized solution of lead acetate precursor together with dopants or additives (if any) desired in the thin film to be deposited.
  • step P 6 the final mixture of P 5 is filtered to form a stock solution as shown in P r Table I below presents a more detailed analysis of steps P.*-P r
  • steps P 1 through P 8 are conventional steps utilized in forming sol-gels used in conventional spin-on thin film forming procedures.
  • step P p the conventional stock solution of P 7 or the conventional hydroryzed solution of P a are modified for use in the deposition processes of the present invention.
  • step P 9 essentially involves adjusting the concentration of the desired chemical compound in the sol-gel, or other stabilized liquid source, such that small droplets of the vaporized source (mist) as flowed into the vacuum chamber
  • the sol-gel concentration will be adjusted such that a film of the sol- gel will deposit completely over the substrate 5 before a significant amount of drying of the individual droplets occur, which would undesirably result in the creation of small disconnected particles on the substrate, the particles ultimately resulting in a thin film which is very porous and or granular.
  • Determination of ihe appropriate concentration of chemical compound in the sol-gel or other stabilized liquid source involves considerations of the particular chemical compound and solvent used in the stabilized liquid source, as well as of the vacuum level maintained within the vacuum chamber 2.
  • solvents having relatively high boiling points such as 2-methoxyethanol used in the PZT sol-gel discussed above, are slower to dry than solvents having relatively low boiling points such as methanol; while higher vacuum levels result in faster drying of any given stabilized liquid source.
  • the stock solution of P 7 or the hydroryzed solution of P 8 will be modified in step P 9 by the addition of 10-15 percent (by volume) of methanol.
  • the normal sol-gel is diluted to a sufficient degree to assure that the small droplets of the vaporized source which deposit on the substrate 5 are sufficiently fluid to spread out and interconnect to form a continuous, uniform film as discussed above.
  • step P 10 the modified solution of step P 9 is vaporized using a source generator such as shown in Figs. 4 or 5, and is flowed into the deposition apparatus 1 through the manifold assembly 40 where it is deposited on the substrate 5 to form a thin film of the sol-gel.
  • the thickness of the deposited thin film will be continuously monitored by conventional means (not shown).
  • the substrate 5 having a thin film of the sol-gel or other stabilized liquid source thereon is subjected to vacuum to remove the solvent from the sol-gel, thus leaving a thin film of the desired chemical compound on the substrate, while at step P 12 the thin film of the chemical compound will, if necessary, be annealed.
  • drying step P ⁇ r drying of the sol-gel film may alternatively be accomplished by using a heating means to bake or otherwise heat the deposited film.
  • P 12 may be effected within the vacuum chamber 2 using appropriate heating means or may be performed in different apparatus outside of the vacuum chamber 2.
  • the substrate having a thin film of the chemical compound thereon is further processed, such as by having a top electrode deposited thereon.
  • the apparatus of the first embodiment of the present invention as discussed above in relation to Figs.1-5 is very advantageous because it effectively combines the best of vacuum, CVD, and wet chemistry (sol-gel, MOD, etc.) techniques to readily produce very complex, multi-element films in a controlled environment.
  • Some specific advantages include the ability to carefully, consistently control the sto hiometiy of thin films being deposited, the relative ease with which stabilized liquid sources may be generated and handled, the ability to keep the deposited films free from contaminants (because the deposition process is operated under vacuum conditions), the ability to form very thin, uniform films fully covering a substrate surface, etc.
  • the deposition process according to the invention will be conducted at room/ambient temperatures.
  • an aspect of the invention is that the stabilized compound sources are agitated ultrasonically to atomize the sources before they are introduced into the process chamber. Depending upon the particular stabilized source and application, it may be desirable to heat the lines through which the vapor is introduced into the manifold assembly and/or into the process chamber.
  • a solvent exchange technique arrives at a common solvent in order to produce a sol-gel or other stabilized liquid having compounds X and Y.
  • the invention is advantageous in depositing complex, compound thin films of materials such as ferroelectrics, super-conductors, materials with high dielectric constants, gems, etc., but is not limited to depositing such complex thin films.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Chemically Coating (AREA)
  • Electrodes Of Semiconductors (AREA)

Abstract

A method and apparatus (1) are disclosed for forming thin films of chemical compounds on substrates (5) in a vacuum chamber (2). The method includes steps of forming at least one stabilized solution of a desired chemical compound and a solvent, providing a substrate (5) within a vacuum deposition chamber (2), producing a mist of the stabilized solution using an ultrasonic device (46), and flowing the mist into the deposition chamber (2) in close proximity to the substrate using a unique nozzle device (8, 10) such that the mist deposits and forms a layer of the stabilized solution on the substrate (5).

Description

METHODS AND APPARATUS FOR MATERIAL DEPOSITION
Field of the Invention
The invention relates to methods for depositing high quality films of complex (compound) materials on substrates at high deposition rates, and apparatus for effecting such methods. Particularly, the invention relates to nonreactive chemical vapor deposition (CVD) methods and apparatus for depositing high quality, stoichiometrically-correct, thin films of a large variety of complex compounds at high deposition rates utilizing stabilized liquid compound sources.
Description of Relevant .Art
There are known methods for depositing thin films of complex compounds such as metal oxides, ferroelectrics, super-conductors, materials with high dielectric constants, gems, etc. Such known methods include: vacuum evaporation (i.e., E-beam, laser ablation, etc.); vacuum sputtering (i.e., E-beam, D.C., R.F., ion-beam, etc.); powder metallurgy; reactive chemical vapor deposition; and liquid application methods (i.e., spin-on techniques, dipping and spraying). .All of such known methods, however, have significant disadvantages associated therewith. The present invention has been developed to overcome the many problems and disadvantages associated with known deposition techniques for depositing thin films of complex chemical compounds including those discussed above, and to generally fulfill a great need in the art by providing a production worthy process which can be used for easily and economically producing thin films (from a few angstroms to microns in thickness) of various complex materials such as ferroelectrics, superconductors, and metal oxides. Brief Description of the Drawings
Fig. 1 is a schematic view of a CVD apparatus according to a first embodiment of the invention. Fig. 2 is an enlarged plan view of a nozzle assembly and an exhaust assembly used in the embodiment of Fig. 1. Fig.3 is an enlarged schematic view of a manifold system used in the first and second embodiments of the invention.
Fig. 4 is a vertical cross sectional view of a preferred apparatus for forming a mist of a stabilized solution according to the present invention. Figs. 5a and 5b show modifications of the apparatus of Fig. 4.
Fig. 6 is a schematic flow chart showing the preparation of a stabilized solution to be used in forming a thin film of lead zirconium titanate according to the present invention. Detailed Description of The Invention .According to a primary aspect of the present invention, stabilized sources or stabilized solutions of desired chemical compounds will initially be prepared and then mists or vapors of the solutions will be generated, flowed into a deposition chamber and deposited in thin films/layers on substrates disposed within the deposition chamber. Such stabilized solutions include at least all of those used in known liquid application techniques and specifically include sol-gels (which include alcohols as the solvent base thereof), metallorganic decomposition (MOD) formulations (which utilize n-decanoic acid as the solvent base thereof), solutions having water as the solvent base thereof, solutions having carboxylic acid as the solvent base thereof, etc. The term "stabilized source" as used herein is intended to designate a source which is obtained by mixing precursors for each element using sol-gel techniques, or other wet chemistry mixing techniques, which lead to a common solvent, and then using the solution having that common solvent as the sole source for the entire compound. Other sources may also be used in parallel for doping or modifying the compound. In the stabilized source the elements are already in the compound in solution with the common solvent or metallorganic precursor.
Use of the stabilized solutions is highly desirable for many reasons. First, the sources themselves are relatively easy to generate, even for complex compounds. In this regard, there is an extensive amount of published literature available detailing various sol-gel preparation techniques, MOD formulation techniques, etc. used in relation to the known liquid application methods of forming thin films, as discussed above. One such publication, Process Optimization and Characterization of Device Worthy Sol-gel Based PZT for Ferroelectric Memories is authored by two of the present inventors and others and appears in FERROELECTRICS, Vol. 109. The complete disclosure of the discussed publication is incorporated herein by reference thereto.
Further, the stabilized solutions used in the present invention are substantially less toxic and easier to handle than the corresponding reactants which are used in conventional, reactive CVD methods as discussed above, whereby the stabilized solutions can be handled and processed at substantially lower cost than the corresponding reactants.
Moreover, use of the stabilized compound sources assures high quality of the thin films produced thereby because the stabilized source can be accurately and consistently produced such that the desired chemical compound contained therein is uniformly, stoichiometricalh/ correct, and because the deposition methods of the present invention do not involve any chemical reactions which might destabilize the chemical compound of its predetermined molecular formulation. Instead, thin films of the stabilized source are directly deposited on substrates from a mist/vapor under vacuum at ambient temperatures and subsequently dried. Referring to Fig. 1, there is shown a thin film deposition apparatus according to a preferred embodiment of the invention, the apparatus being generally designated at 1. The apparatus 1 generally comprises a vacuum chamber 2, a substrate holder 4, a barrier plate 6, a nozzle assembly 8, and an exhaust assembly 10. The vacuum chamber 2 includes a main body 12, a lid 14 which is securable over the main body to define an enclosed space within the vacuum chamber, and the chamber is connected to an appropriate vacuum source (not shown) as generally indicated at 16. The lid 14 is preferably pivotally connected to the main body 12 using a hinge as indicated at 18.
The substrate holder 4 is preferably supported on a rotatable shaft 20 which is in turn connected to a motor (not shown) so that the holder may, if desired, be rotated during a deposition process. Indicated at 22 is an insulating connector which electrically insulates the substrate holder 4 and a substrate 5 supported thereon from the rest of the deposition apparatus 1 so that a DC or AC (RF) bias can be created between the substrate holder 4 and the barrier plate 6, if desired, utilizing the DC/RF feedthrough indicated at 23. Such a DC bias could be utilized, for example, for field-poling of thin films as they are being deposited on the substrate 5. For effecting such a DC bias an electrical source (not shown) would be operativery connected across the barrier 6 and the substrate holder 4.
The barrier plate 6 is preferably made of an electrically conductive material such as stainless steel, and is of sufficiently large size to extend completely over the substrate 5 in parallel thereto so that a vaporized source or mist as injected by the nozzle assembly 8 is forced to flow between the plate 6 and the substrate holder 4 over the substrate 5. As depicted, the barrier plate 6 is preferably connected to the lid 14 by a shaft 24 so that the plate 6 will be moved away from the substrate 5 whenever the lid is opened. The shaft 24 is preferably adjustable in length so that the spacing between the holder 4 and the plate 6 can be adjusted depending on the source materials, the flow rate, etc. For example, the spacing may be adjustable to define a spacing in the range of 2 - 50 mm.
The nozzle assembly 8 and the exhaust assembly 10 are more particularly shown with reference to Fig. 2. As depicted, the nozzle assembly 8 preferably includes an input tube 26 which receives a vaporized source from a manifold assembly 40 as discussed below in relation to Fig. 3, and an arcuate nozzle tube 28 having a plurality of small holes with removable screws 30 provided in a uniformly spaced manner along a surface of the tube 28 facing inwardly of the deposition chamber 2. The screws 30 can be selectively removed depending on the stabilized source, flow rate, etc. to adjust the flow of the vaporized source over the substrate 5. Indicated at 32 are end caps of the tube 28. The structure of the exhaust assembly 10 is substantially the same as that of the nozzle assembly 8, except that a pipe 34 leads to a vacuum/exhaust source (not shown). As depicted, the arcuate tube 28 of the nozzle assembly 8 and the corresponding arcuate tube of the exhaust assembly 10 will preferably surround respective, oppositely disposed peripheral portions of the substrate 5, and the arcuate tubes will be spaced from each other across a central or intermediate portion of the substrate 5. Through such structure, and by adjusting the location of open holes in the two arcuate tubes, the flow of a vaporized source or mist over the substrate 5 can be well controlled for various sources, various flow rates, etc., for thereby achieving a uniform deposition of a thin film on the substrate 5.
Referring to Figs. 1 and 2, the substrate holder 4, the barrier plate 6, the nozzle assembly 8 and the exhaust assembly 5 collectively cooperate to define a relatively small deposition cavity surrounding an upper/exposed surface of the substrate 5, and within which the vaporized source is substantially contained throughout the deposition process.
.Although preferred embodiments of the substrate holder, the barrier plate, the nozzle assembly and the exhaust assembly are shown and described, it will be understood that variations of such structures can be utilized within the scope of the present invention. For example, the arcuate nozzle and exhaust tubes could be replaced with tubes of other structures such as V-shaped or U-shaped, or could simply be replaced by a plurality of separate nozzles and separate exhaust ports.
Referring to Fig. 3, there is shown a manifold assembly 40 according to the present invention. The manifold assembly -40 is utilized for supplying a vaporized source to the nozzle assembly 8, and generally comprises a mixing chamber 42, a plurality of inlets 44 which are connected to corresponding source generators 46 through respective valves 48, a valve 50 for regulating flow from the mixing chamber 42 to the nozzle assembly 8, and an exhaust valve 52. In use, one or more of the source generators 46 are utilized to generate one or more different vaporized sources or mists which are then flowed into the mixing chamber 42 through the valves -48 and inlets 44. The vaporized sources as flowed into the mixing chamber 42 are mixed to form a single, uniform vaporized source or mist, which is then flowed into the vacuum chamber 2 at an appropriate flow rate through the valve 50. The valve 50 can be selectively closed off so that the vacuum chamber 2 can be pumped down to dry a deposited film of a stabilized liquid source, or to clean and purge the system when necessary. Similarly, the outlet of the exhaust valve 52 is connected to a vacuum source (not shown) so that, when necessary to exhaust purge one or more of the mist generators 46, the valve 50 can be closed off, the valve 52 and one or more of the valves -48 can be opened, and the mixing chamber 42 can be pumped down to clean and purge the source generators) and the mixing chamber.
It is preferred that a mist will be flowed from the manifold assembly 40 into the nozzle assembly 8 at ambient temperature or slightly above room temperature.
Referring to Fig. 4, there is shown a preferred source generator 46 according to the invention. The generator 46 includes a closed container 54, an ultrasonic transducer 56 fluid-tightly sealed into the bottom of the container 54, a valve 58 for introducing a stabilized liquid source such as a sol-gel or an MOD formulation into the container 54 while the container is maintained under sealed, vacuum-tight conditions, and an inlet port 60 and an outlet port 62 for passing a carrier gas through the container 54. In use, a stabilized liquid source 64 will be introduced into the container 54 through the valve 58 up to an appropriate level as measured by a level-detecting means (not shown), the transducer 56 is activated to generate a mist 66 of the stabilized liquid source, and an appropriate carrier gas is passed through the mist 66 via the ports 60, 62 where it becomes wet or saturated with the mist, and the wet carrier gas is then passed from the outlet port 62 into the manifold assembly -40 as discussed above. The carrier gas will normally, be an inert gas such as argon or helium, but may comprise a reactive gas in appropriate situations. The valve 58 will be selectively actuated as necessary to maintain the stabilized liquid source 64 at an appropriate level within the container 54.
The preferred source generator -46 as shown in Fig. 4 is particularly advantageous because it creates a vaporized source which can be effectively flowed or injected into the vacuum deposition chamber 2 without complications such as freezing. Referring to Fig. 5a there is shown a source generator -46' which is modification of the source generator 46 shown in Fig. 4 whereby the ultrasonic transducer 56 does not come into contact with the stabilized liquid source 64. Instead, the stabilized liquid source 64 is contained within a first, closed container 54' while the transducer 56 is sealingly fitted to a bottom wall of a second, open container 68, a working medium 70 such as water or another liquid is disposed in the second container 68 over the transducer, and the first container 54' is disposed in spaced relation above an upper surface of the working medium 70 such that a mist plume 72 of the working medium created by the ultrasonic transducer contacts a bottom wall of the first container 54' for thereby creating the mist 66 of the stabilized liquid 64 within the first container 54', which is then flowed into the manifold assembly 40 in the same manner as discussed above in relation to Fig. 4. The modified source generator -46' shown in Fig. 5 has all of the advantages of the source generator 46 shown in Fig. 4, as well as an additional advantage that the ultrasonic transducer 56 does not become contaminated with a stabilized liquid used to form a desired thin film.
Referring to Fig. 5b there is shown another modification of the mist generating apparatus of Fig.4. The modification of Fig.5b is very similar to that of Fig. 4 except that the transducer 56 is suspended in the generator 46" above the stabilized liquid source rather than being sealed into the bottom wall of the container.
.Although the source generators 46, 46', 46" shown in Figs. 4, 5a and 5b are preferred according to the invention, it will be understood that other source generators could be utilized according to the invention. For example, a stabilized liquid source could be provided within a closed container and an appropriate carrier gas could be simply bubbled through the stabilized liquid and then flowed into the mixing chamber 40; or a spray nozzle could be used to generate a mist of a stabilized liquid source within a closed container, and an appropriate carrier gas could be flowed through the mist and into the mixing chamber 40 using an inlet and outlet port similar to the ports 60, 62 shown in Fig. 4.
An example of the sol-gel synthesis of YMn03 follows. 1 gm. of yttrium isopropoxide Y[OCH(CH3)2]3 was mixed with 8 ml. of 2-methoxyethanol. The yttrium isopropoxide did not go into solution, but was forced into solution by the addition of approximately 25 drops (slightly over one ml.) of hydrochloric acid. 0.25 grams of manganese acetate Mn(OOCCH3)2-H20 was mixed with 5 ml. 2-methαxyethanol. The manganese acetate would not dissolve in the 2- methαxyethanol, but was forced into solution by the addition of approximately 10 drops of hydrochloric acid. The yttrium and manganese solutions were then mixed together at room temperature resulting in a slightly yellow colored solution. The resulting YMn03 solution did not form a film when spun onto a silicon wafer. Adding H20 for hydrolysis did not improve the film-forming characteristics. However, the addition of approximately 25 drops of titanium isopropoxide (a gel former) to the yttrium manganese solution resulted in a solution which remained clear for approximately 3 hours and formed good films when spun onto a silicon wafer.
Referring to Fig. 6, there is shown an exemplary flow chart depicting the preparation of a stabilized liquid solution of lead zirconium titanate (PZT hereinafter) to be deposited utilizing the apparatus of Figs. 1-5. At steps P«,-P3 stabilized liquid precursors of titanium isopropoxide, zirconium N-propoxide and lead acetate are respectively formed utilizing 2-methoxyethanol as the common solvent of each of the precursors. At step P4 the stabilized solutions of titanium isopropoxide and zirconium n-propoxide are mixed, while at step P5 such mixture is further mixed with the stabilized solution of lead acetate precursor together with dopants or additives (if any) desired in the thin film to be deposited. At step P6 the final mixture of P5 is filtered to form a stock solution as shown in Pr Table I below presents a more detailed analysis of steps P.*-Pr
TAKE I
SO.L-GEL PZT SOLUTION PROCESS FLOW SHEET
100 STOICHIOMETRY
110 Pb: 94.7 gm Pb(Ac)2 • 3^0 = 0.25 moles Pb. 120 Zr: 46.8 gm Zr n-propaxide(30% propanol by weight) = 0.10 moles Zr.
130 Ti: 42.6 gm Ti-isopropoxide = 0.15 moles Ti.
140 10:1 mole ratio (moles 2-methoxyethanol:moles metal). 200 LEAD PRECURSOR 210 94.73 gm Pb(Ac)2 • 3HzO is added to 197 ml 2-methoκyethanol.
220 Distill solution to a final vapor temperature of 114*C.
230 Amount of final distillate: 107 ml. 00 ZIRCONIUM PRECURSOR
310 46.82 gm .Zr n-propoxide in propanol is added to 79 ml 2-methoxyethanol.
320 Distill solution to a final vapor temperature of 113*C.
330 Amount of final distillate: 79 ml. 00 TITANIUM PRECURSOR
410 42.62 gm Ti-isopropoxide is added to 118 ml 2-methoxyethanol. 420 Distill solution to a final vapor temperature of 114"C.
430 .Amount of final distillate: 76 ml. 00 MIXING OF PRECURSORS
510 Add Ti precursor to Zr precursor and stir.
520 Add TiZr solution to Pb solution and stir for h hour(s). 530 .Amount of PZT stock solution: 250 ml.
540 Filter PZT stock solution through an appropriate size syringe filter.
550 Molarity of solution: 1.0 M (moles PZT/1 of solution). At step P8 the stock solution of P7 is hydro yzed using acetic acid and
HzO or other appropriate materials, although such hydroryzation step may be omitted as indicated by the dotted line extending from P7 to P9. The steps P1 through P8 are conventional steps utilized in forming sol-gels used in conventional spin-on thin film forming procedures.
At step Pp the conventional stock solution of P7 or the conventional hydroryzed solution of Pa are modified for use in the deposition processes of the present invention.
Such step P9 essentially involves adjusting the concentration of the desired chemical compound in the sol-gel, or other stabilized liquid source, such that small droplets of the vaporized source (mist) as flowed into the vacuum chamber
2 will deposit onto the substrate 5, spread out and interconnect to form a uniform film of the sol-gel over the entire upper surface of the substrate 5. In other words, the sol-gel concentration will be adjusted such that a film of the sol- gel will deposit completely over the substrate 5 before a significant amount of drying of the individual droplets occur, which would undesirably result in the creation of small disconnected particles on the substrate, the particles ultimately resulting in a thin film which is very porous and or granular. Determination of ihe appropriate concentration of chemical compound in the sol-gel or other stabilized liquid source involves considerations of the particular chemical compound and solvent used in the stabilized liquid source, as well as of the vacuum level maintained within the vacuum chamber 2. For example, solvents having relatively high boiling points, such as 2-methoxyethanol used in the PZT sol-gel discussed above, are slower to dry than solvents having relatively low boiling points such as methanol; while higher vacuum levels result in faster drying of any given stabilized liquid source.
With the deposition of PZT from a sol-gel as prepared in the manner discussed above, and with the vacuum chamber 2 operating at a vacuum of 570-575 Torr, it is preferred that the stock solution of P7 or the hydroryzed solution of P8 will be modified in step P9 by the addition of 10-15 percent (by volume) of methanol. In other words, the normal sol-gel is diluted to a sufficient degree to assure that the small droplets of the vaporized source which deposit on the substrate 5 are sufficiently fluid to spread out and interconnect to form a continuous, uniform film as discussed above.
.Although methanol is the preferred diluent for the sol-gel of PZT according to the present invention, it will be understood that other diluents
(including 2-methoxyethanol) could be used for diluting the sol-gel of PZT, and that various other diluents would be utilized with other sol-gels and with other stabilized liquid sources used according to the present invention.
At step P10 the modified solution of step P9 is vaporized using a source generator such as shown in Figs. 4 or 5, and is flowed into the deposition apparatus 1 through the manifold assembly 40 where it is deposited on the substrate 5 to form a thin film of the sol-gel. The thickness of the deposited thin film will be continuously monitored by conventional means (not shown).
At drying step P., , the substrate 5 having a thin film of the sol-gel or other stabilized liquid source thereon is subjected to vacuum to remove the solvent from the sol-gel, thus leaving a thin film of the desired chemical compound on the substrate, while at step P12 the thin film of the chemical compound will, if necessary, be annealed. In drying step Pιr drying of the sol-gel film may alternatively be accomplished by using a heating means to bake or otherwise heat the deposited film. Further, with many complex thin films, such as ferroelectrics, it is necessary to activate the dried thin film by annealing before the films will function in a desired manner. The drying and annealing steps P1V
P12 may be effected within the vacuum chamber 2 using appropriate heating means or may be performed in different apparatus outside of the vacuum chamber 2.
At step P13 the substrate having a thin film of the chemical compound thereon is further processed, such as by having a top electrode deposited thereon. The apparatus of the first embodiment of the present invention, as discussed above in relation to Figs.1-5 is very advantageous because it effectively combines the best of vacuum, CVD, and wet chemistry (sol-gel, MOD, etc.) techniques to readily produce very complex, multi-element films in a controlled environment Some specific advantages include the ability to carefully, consistently control the sto hiometiy of thin films being deposited, the relative ease with which stabilized liquid sources may be generated and handled, the ability to keep the deposited films free from contaminants (because the deposition process is operated under vacuum conditions), the ability to form very thin, uniform films fully covering a substrate surface, etc.
As indicated by the structure of the deposition apparatus 1 shown in Fig.
1, i.e., the lack of any heating means therein, it is preferred that the deposition process according to the invention will be conducted at room/ambient temperatures. As discussed above in relation to Figs.4 and 5, an aspect of the invention is that the stabilized compound sources are agitated ultrasonically to atomize the sources before they are introduced into the process chamber. Depending upon the particular stabilized source and application, it may be desirable to heat the lines through which the vapor is introduced into the manifold assembly and/or into the process chamber.
.Another aspect of the invention involves a solvent exchange technique.
Many times a compound X will dissolve in one particular solvent only and no other solvent Similarly, a compound Y may dissolve in a different solvent and the solvent for compound X is not compatible with the solvent for compound Y. With the present invention, a solvent exchange technique arrives at a common solvent in order to produce a sol-gel or other stabilized liquid having compounds X and Y.
The invention is advantageous in depositing complex, compound thin films of materials such as ferroelectrics, super-conductors, materials with high dielectric constants, gems, etc., but is not limited to depositing such complex thin films.
Although there has been described what is at present considered to be the preferred embodiment of the present invention, it will be understood that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiment is, therefore, to be considered in all aspects as illustrative and not restrictive. The scope of the invention is indicated by the appended claims rather than the
foregoing description.

Claims

WE CLAIM: 1. A method of forming a thin film of a chemical compound on a
substrate, comprising the steps of: forming at least one stabilized solution of a chemical compound and a solvent; providing a substrate within an enclosed deposition chamber; producing a mist of said stabilized solution; and flowing the mist into the deposition chamber such that the mist deposits and forms a film of the stabilized solution on an exposed surface of the substrate.
2. A method according to claim 1, including a further step of drying said deposited film of the stabilized solution to remove the solvent therefrom.
3. A method according to claim 1, wherein said deposition chamber is maintained at substantially ambient temperature and under vacuum and said mist is flowed into said deposition chamber at substantially ambient temperature.
4. A method according to claim 1, wherein said mist as flowed into the deposition chamber is contained within a small cavity surrounding said exposed surface of said substrate. 5. A method according to claim 1, wherein said mist is flowed into said deposition chamber from a plurality of ports disposed in close proximity around one peripheral portion of said substrate, and said mist is drawn off by a plurahty of exhaust ports disposed in close proximity around another peripheral portion
of said substrate opposite to said one peripheral portion.
6. A method according to claim 3, wherein a concentration of said chemical compound in said stabilized solution is controlled in dependence on the temperature and the vacuum level within said deposition chamber such that mist droplets of said stabilized solution which deposit on said substrate spread out and interconnect to form a uniform film.
7. Apparatus for depositing a thin film on a substrate, comprising: a deposition chamber having an enclosed space therein; means for supporting a substrate within said deposition chamber; means for producing a mist of a stabilized solution of a chemical compound; and means for flowing said mist into said deposition chamber such that the mist deposits and forms a thin film of the stabilized solution on said substrate.
8. Apparatus according to claim 7, including means for maintaining said deposition chamber under vacuum. 9. .Apparatus according to claim 7, including means for containing a mist as flowed into the deposition chamber within a small portion of the enclosed space inside the deposition chamber surrounding an exposed surface of said substrate.
10. .Apparatus according to claim 9, wherein said containing means includes a substrate holder supporting said substrate thereon and a barrier plate disposed in spaced relation above said substrate holder in parallel thereto.
11. Apparatus according to claim 10, wherein said containing means further includes a nozzle assembly disposed in close proximity around one peripheral portion of said substrate and an exhaust assembly disposed in close proximity around another peripheral portion of said substrate opposite to said one peripheral portion.
12. .Apparatus according to claim 7, including means for rotating said substrate during a deposition process; and said mist flowing means includes a plurality of nozzle ports disposed around one peripheral portion of said substrate and adapted to flow said mist in parallel over said exposed surface of said substrate.
13. Apparatus according to claim 12, including means for exhausting mist after it is flowed over said substrate, said exhausting means including a plurality of exhaust ports disposed in close proximity around another peripheral portion of said substrate opposite to said one peripheral portion of said substrate. AMENDED CLAIMS
[received by the International Bureau on 14 August 1992 (14.08.92); new claim 14 added; original claims 1,2,4-12 amended; remaining claims unchanged (4 pages)] 1. A method of forming a thin film of a chemical compound on a substrate, comprising the steps of: forming at least one stabilized metalorganic solution of a desired chemical compound and a solvent, said solution containing a substantially stoichiometrically-correct quantity of said chemical compound; providing a substrate within an enclosed deposition chamber; producing a mist of said stabilized solution; flowing the mist into the deposition chamber such that the mist deposits and forms a thin uniform film of the stabilized solution on an exposed surface of the substrate; and drying the thin film of said stabilized solution to remove organic matter therefrom.
2. A method according to claim 1, including a further step of maintaining an electrical bias within a small portion of said enclosed space surrounding said exposed surface of said substrate.
3. A method according to claim 1, wherein said deposition chamber is maintained at substantially ambient temperature and under vacuum during the mist flowing step and said mist is flowed into said deposition chamber at substantially ambient temperature.
4. A method according to claim 3, wherein a concentration of said chemical compound in said stabilized metalorganic solution is controlled in dependence on the temperature and the vacuum level within said deposition chamber such that mist droplets of said stabilized solution which deposit on said substrate spread out and interconnect to form said uniform thin film.
5. A method according to claim 1, wherein said mist is flowed into said deposition chamber from a plurality of ports disposed in close proximity around one peripheral portion of said substrate, and said mist is drawn off by a plurality of exhaust ports disposed in close
proximity around another peripheral portion of said substrate opposite to said one peripheral portion; and said method includes further steps of supporting said substrate on a rotatable holder and providing a barrier plate in narrowly spaced relation parallel to said exposed surface of said substrate such that said barrier plate, said holder, said nozzle assembly and said exhaust assembly define a small cavity surrounding said exposed surface of said substrate.
6. A method according to claim 1, including a further step of containing said mist as flowed into the deposition chamber within a small cavity surrounding said exposed surface of said substrate.
7. Apparatus for depositing a thin film of a chemical compound on a substrate, comprising: a deposition chamber having an enclosed space therein; means for supporting a substrate within said deposition chamber; means for producing a mist of a stabilized metalorganic solution containing a substantially stoichiometrically-correct quantity of a desired chemical compound; means for flowing said mist into said deposition chamber such that the mist deposits and forms a thin uniform film of the stabilized solution on an exposed surface of said
substrate; and means for drying said thin film of said stabilized solution to remove organic matter therefrom.
8. Apparatus according to claim 7, including means for maintaining said deposition chamber under vacuum and means for maintaining the deposition chamber at substantially ambient temperature when the mist is being flowed therein.
9. Apparatus according to claim 7, including means for containing a mist as flowed into the deposition chamber within a small portion of the enclosed space inside the deposition chamber surrounding said exposed surface of said substrate.
10. Apparatus according to claim 9, wherein said containing means includes a substrate holder supporting said substrate on one surface of the holder and a barrier plate disposed in a narrowly spaced relation parallel to said substrate holder and facing said substrate.
11. Apparatus according to claim 10, wherein said containing means further includes a nozzle assembly disposed in close proximity around one peripheral portion of said substrate and an exhaust assembly disposed in close proximity around another peripheral portion of said substrate opposite to said one peripheral portion, said substrate holder, said barrier plate, said nozzle assembly and said exhaust assembly collectively defining said small portion of said enclosed space.
2S 12. Apparatus according to claim 7, including means for rotating said substrate during a deposition process; said mist flowing means includes a plurality of nozzle ports disposed around one peripheral portion of said substrate and adapted to flow said mist in parallel over said exposed surface of said substrate; and a barrier plate disposed in narrowly spaced relation parallel to said exposed surface of said substrate to define a narrow gap therebetween.
13. Apparatus according to claim 12, including means for exhausting said mist after it is flowed over said substrate, said exhausting means including a plurality of exhaust ports disposed in close proximity around another peripheral portion of said substrate opposite to said one peripheral portion of said substrate.
14. Apparatus according to claim 7, including means for maintaining an electrical bias within a small portion of said enclosed space surrounding said exposed surface of said
substrate.
.
STATEMENT UNDER ARTICLE 19
Independent claims 1 and 7 have been amended to define that the stabilized solution is a metalorgamc solution containing a substantially stoichiometrically-correct quantity of a
desired compound, that the mist of the solution forms a thin uniform film on an exposed surface of the substrate and that the film or solution is dried to remove organic matter
therefrom.
Claim 2 and new claim 14 define a step/means for maintaining an electrical bias in a small space surrounding the substrate.
Claim 5 is amended to further define the rotatable substrate holder, the barrier plate, and the cavity defined by the holder, the barrier plate, and the nozzle and exhaust assemblies.
Claim 8 is amended to define means for maintaining the deposition chamber and substantially ambient temperature; claim 12 is amended to define the barrier plate; the number of claims 4 and 6 has been reversed such that original claim 4 is now claim 6 and vice versa; and the language of claims 4, 6, 9 and 10 has been slightly amended to overcome
minor informalities.
Claim 11 is amended to define the collective function of the substrate holder, the barrier plate, nozzle assembly in the exhaust assembly collectively define the small portion of the enclosed space.
.All of the claim amendments are fully supported in the disclosure of the originally
filed application.
PCT/US1992/001380 1991-02-25 1992-02-21 Methods and apparatus for material deposition WO1992015112A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1019930702549A KR100202532B1 (en) 1991-02-25 1992-02-21 Electronic parts of electronic device and process for fabricating the same and apparatus therewith
JP4511586A JP2860505B2 (en) 1991-02-25 1992-02-21 Material deposition equipment

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US66042891A 1991-02-25 1991-02-25
US660,428 1991-02-25

Publications (1)

Publication Number Publication Date
WO1992015112A1 true WO1992015112A1 (en) 1992-09-03

Family

ID=24649498

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/001380 WO1992015112A1 (en) 1991-02-25 1992-02-21 Methods and apparatus for material deposition

Country Status (4)

Country Link
JP (2) JP2860505B2 (en)
KR (1) KR100202532B1 (en)
AU (1) AU2013992A (en)
WO (1) WO1992015112A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5456945A (en) * 1988-12-27 1995-10-10 Symetrix Corporation Method and apparatus for material deposition
US5614252A (en) * 1988-12-27 1997-03-25 Symetrix Corporation Method of fabricating barium strontium titanate
US7018676B2 (en) 2000-03-29 2006-03-28 Seiko Epson Corporation Method and device for manufacturing ceramics, semiconductor device and piezoelectric device
FR2897281A1 (en) * 2006-02-14 2007-08-17 Saint Louis Inst Continuously producing pure nanocrystalline compounds or mixtures, e.g. explosives, by evaporating mist of solution or dispersion droplets and trapping obtained nanoparticles with electrostatic separator
US9150961B2 (en) 2009-11-16 2015-10-06 Fei Company Gas delivery for beam processing systems

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111744732B (en) * 2020-07-09 2021-07-13 电子科技大学 Vacuum spin coating device for deep hole side wall adhesion layer of glass adapter plate

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3473959A (en) * 1964-08-10 1969-10-21 Licentia Gmbh Method for coating semiconductors and apparatus
US3880112A (en) * 1971-10-20 1975-04-29 Commissariat Energie Atomique Device for the preparation of thin films
US4290384A (en) * 1979-10-18 1981-09-22 The Perkin-Elmer Corporation Coating apparatus
US4508054A (en) * 1981-03-06 1985-04-02 Battelle Memorial Institute Device for depositing a mineral oxide coating on a substrate
US4650539A (en) * 1980-05-27 1987-03-17 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Manufacture of cadmium mercury telluride
US4689247A (en) * 1986-05-15 1987-08-25 Ametek, Inc. Process and apparatus for forming thin films
US4783006A (en) * 1986-07-09 1988-11-08 President Of Kogyo Gijutuin Mist supplying device for forming thin film
US5041229A (en) * 1988-12-21 1991-08-20 Board Of Regents, The University Of Texas System Aerosol jet etching
US5069157A (en) * 1989-08-31 1991-12-03 Taiyo Yuden Co., Ltd. Thin film forming apparatus

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3473959A (en) * 1964-08-10 1969-10-21 Licentia Gmbh Method for coating semiconductors and apparatus
US3880112A (en) * 1971-10-20 1975-04-29 Commissariat Energie Atomique Device for the preparation of thin films
US4290384A (en) * 1979-10-18 1981-09-22 The Perkin-Elmer Corporation Coating apparatus
US4650539A (en) * 1980-05-27 1987-03-17 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Manufacture of cadmium mercury telluride
US4508054A (en) * 1981-03-06 1985-04-02 Battelle Memorial Institute Device for depositing a mineral oxide coating on a substrate
US4689247A (en) * 1986-05-15 1987-08-25 Ametek, Inc. Process and apparatus for forming thin films
US4783006A (en) * 1986-07-09 1988-11-08 President Of Kogyo Gijutuin Mist supplying device for forming thin film
US5041229A (en) * 1988-12-21 1991-08-20 Board Of Regents, The University Of Texas System Aerosol jet etching
US5069157A (en) * 1989-08-31 1991-12-03 Taiyo Yuden Co., Ltd. Thin film forming apparatus

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5456945A (en) * 1988-12-27 1995-10-10 Symetrix Corporation Method and apparatus for material deposition
US5614252A (en) * 1988-12-27 1997-03-25 Symetrix Corporation Method of fabricating barium strontium titanate
US7018676B2 (en) 2000-03-29 2006-03-28 Seiko Epson Corporation Method and device for manufacturing ceramics, semiconductor device and piezoelectric device
FR2897281A1 (en) * 2006-02-14 2007-08-17 Saint Louis Inst Continuously producing pure nanocrystalline compounds or mixtures, e.g. explosives, by evaporating mist of solution or dispersion droplets and trapping obtained nanoparticles with electrostatic separator
US9150961B2 (en) 2009-11-16 2015-10-06 Fei Company Gas delivery for beam processing systems

Also Published As

Publication number Publication date
JPH11131247A (en) 1999-05-18
JPH06508659A (en) 1994-09-29
JP3238663B2 (en) 2001-12-17
AU2013992A (en) 1992-09-15
JP2860505B2 (en) 1999-02-24
KR930703695A (en) 1993-11-30
KR100202532B1 (en) 1999-06-15

Similar Documents

Publication Publication Date Title
US6511718B1 (en) Method and apparatus for fabrication of thin films by chemical vapor deposition
US5316579A (en) Apparatus for forming a thin film with a mist forming means
US5540772A (en) Misted deposition apparatus for fabricating an integrated circuit
US6110531A (en) Method and apparatus for preparing integrated circuit thin films by chemical vapor deposition
US6056994A (en) Liquid deposition methods of fabricating layered superlattice materials
US6273951B1 (en) Precursor mixtures for use in preparing layers on substrates
US6133161A (en) Methods of forming a film on a substrate using complexes having tris(pyrazolyl) methanate ligands
US6682602B2 (en) Chemical vapor deposition systems including metal complexes with chelating O- and/or N-donor ligands
US6162712A (en) Platinum source compositions for chemical vapor deposition of platinum
US6349887B1 (en) Liquid delivery system
US5962085A (en) Misted precursor deposition apparatus and method with improved mist and mist flow
US5614252A (en) Method of fabricating barium strontium titanate
EP1643003A1 (en) Vaporizer for CVD apparatus
KR20010103563A (en) Misted precursor deposition apparatus and method with improved mist and mist flow
KR100300655B1 (en) Liquid source formation of thin films using hexamethyl-disilazane
US6787186B1 (en) Method of controlled chemical vapor deposition of a metal oxide ceramic layer
JPH07268634A (en) Cvd apparatus for liquid raw material and cvd process using liuqid raw material and the liquid raw material
WO1992015112A1 (en) Methods and apparatus for material deposition
JP2004256510A (en) Bismuth source solution for chemical vapor deposition and method for forming bismuth-containing thin film using the same
KR100480501B1 (en) Process for the formation of pzt thin film by metal-organic chemical vapor deposition
JP2005206874A (en) Iridium-containing film deposition material, and method for producing iridium-containing film
Li et al. Large Area PbZr 1-x Ti x O 3 (PZT) Thin Films Deposited by MOCVD Processes
KR20030020491A (en) Method for the preparation of a pzt thin layer by a metal organic chemical vapor deposition
JP2000252271A (en) Film forming equipment

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU JP KR

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase