WO1989007667A1 - Procedes et appareil de depot de couches minces - Google Patents

Procedes et appareil de depot de couches minces Download PDF

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Publication number
WO1989007667A1
WO1989007667A1 PCT/GB1989/000114 GB8900114W WO8907667A1 WO 1989007667 A1 WO1989007667 A1 WO 1989007667A1 GB 8900114 W GB8900114 W GB 8900114W WO 8907667 A1 WO8907667 A1 WO 8907667A1
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WO
WIPO (PCT)
Prior art keywords
mist
reaction zone
substrate
solution
thin film
Prior art date
Application number
PCT/GB1989/000114
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English (en)
Inventor
Alan Saunders
Original Assignee
Aron Vecht And Company Limited
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 Aron Vecht And Company Limited filed Critical Aron Vecht And Company Limited
Publication of WO1989007667A1 publication Critical patent/WO1989007667A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/408—Oxides of copper or solid solutions thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides
    • C23C16/306—AII BVI compounds, where A is Zn, Cd or Hg and B is S, Se or Te
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
    • H10N60/0436—Processes for depositing or forming copper oxide superconductor layers by chemical vapour deposition [CVD]
    • H10N60/0464—Processes for depositing or forming copper oxide superconductor layers by chemical vapour deposition [CVD] by metalloorganic chemical vapour deposition [MOCVD]

Definitions

  • METHODS AND APPARATUS FOR DEPOSITING THIN FILMS This i nventi on relates to methods and apparatus for depositing thin films. It has application inter al ia in the deposition of thin films of superconducting oxides, especially quaternary compounds of the elements yttrium, barium, copper and oxygen. It also has application in the deposition of thin films of metal-chalcogenide compounds.
  • a method of depositing thin films comprises the steps of generating a fine mist of a solution of a mixture of substances which contain component chemical elements which are required in a resulting thin film, transporting the mist to a reaction zone, decomposing the mist in the reaction zone into its components and depositing the components as a thin film on a substrate.
  • Decomposition of the mist may be achieved by heating, or by a combination of heating and photon or plasma enhanced decomposition.
  • the mist is subjected to a pre-heating step prior to entry into the reaction zone. This avoids the so-called 'spotting' problem associated with the deposition of airborne droplets of varying size.
  • the fine mist may be generated by atomising the solution in a spray head by means of a carrier gas.
  • the carrier gas may be an inert gas or may react with the products of decomposition.
  • the substances in the solution from which the fine mist is generated may be soluble compounds of the class of elements comprising yttrium, scandium and the rare earths, Group IIA elements and Group IB elements, for example soluble compounds of yttrium, barium and copper.
  • the carrier gas may be air or oxygen to enable the component elements to be oxidised when they are deposited.
  • a method of depositing a metal-chalcogenide thin film on a substrate comprises the steps of generating a fine mist of a solution in which an organo-metallie compound including the desired metal and the desired chalcogen is dissolved, transporting the mist to a reaction zone, heating the mist in the reaction zone to crack the compound and release the metal element and the chalcogen element and depositing the products of cracking as a metal chalcogenide on a substrate.
  • apparatus for depositing thin films comprises means for generating a fine mist from a solution of a mixture of substances which contain chemical elements required in a resulting thin film, means for enabling the mist to be transported to a reaction zone, means for heating the mist in the reaction zone so that the substances therein decompose into their components, and means for enabling the components to be deposited as a thin film on a substrate.
  • means are also provided for pre-heating the mist prior to entry into the reaction zone.
  • the means for generating a fine mist may comprise a spray head and means for supplying a carrier gas to the spray head.
  • apparatus for fabricating a metal-chalcogenide thin film on a substrate comprises means for generating a fine mist of a solution in which an organo-metallic compound including the desired metal and the desired chalcogen is dissolved, means for enabling the mist to be transported to a reaction zone, means for heating the mist in the reaction zone to crack the compound and release the metal element and the chalcogen element and means for enabling the products of cracking to be deposited on a substrate to form a thin film of a metal-chalcogenide compound.
  • FIG. 1 illustrates in diagrammatic form apparatus embodying the invention.
  • an apparatus comprising a reservoir 1 for a solution 2.
  • a supply pipe 3 for a carrier gas terminates in an atomising spray head 4 positioned at the top of reservoir 1 above the level of solution 2.
  • Solution 2 can be drawn into spray head 4 through a vertical suction pipe 5 extending almost to the bottom of reservoir 1.
  • An output pipe 6 from reservoir 1 passes through a pre-heater 7 to a reaction chamber 8 heated by a heater 9.
  • a substrate 10 is positioned in reaction chamber 8 and the temperature of substrate 10 is monitored by means of a thermocouple 11.
  • An outlet 12 from chamber 8 is provided for exhaust gases.
  • a carrier gas is supplied under moderate pressure to pipe 1 and draws up the solution 2 into the spray head 4 from which a fine mist of the solution emerges.
  • the mist is transported by the gas flow along pipe 6 where it is heated by preheater 7 to vapourise it and thence it passes into reaction chamber 8.
  • the vapour passes across the heated substrate 10 in chamber 8 it decomposes and its components are deposited as a thin film on substrate 10.
  • the mist may be directed at a heated wire or filament so as to coat the wire with a deposited film.
  • the coating is of a superconducting material, or can be made superconducting by subsequent heat treatment, it is possible to produce continuous lengths of superconductor coated wires or filaments in this manner.
  • the solvent for solution 2 may comprise any suitable solvent depending on the nature of the solute compounds.
  • suitable solvents are alcohols, water, DMF and decalin.
  • solution 2 comprises a solution of a mixture of compounds each containing one or more of the elemental components of the desired oxide.
  • the carrier gas can conveniently be air or oxygen for the subsequent oxidation of the components of the solution after the fine mist has been heated and decomposed.
  • the resulting thin film can comprise a multinary compound comprising one or more of the elements of the following chemical groups in any combination:
  • the solute compounds for solution 2 can be any suitable ones of the following:
  • Group IIA elements Yttrium acetylacetonate or its derivatives, yttrium acetate or its homologues, yttrium halides, yttrium nitrate, yttrium chlorate, or yttrium alkoxides.
  • Group IB elements Barium acetate or any of its homologues, barium acetylacetonate or its derivatives, barium halides, barium 2-ethyl hexanoate, barium nitrate or barium alkoxides.
  • solution 2 containing dissolved compounds of yttrium, barium and copper selected from the above list is heated in reaction chamber 8 in the temperature range 300-1000°C depending on the type of substrate that is employed, e.g. whether it is glass or ceramic and depending on the decomposition temperatures of the source materials.
  • the source material is a solution of a mixture of yttrium, barium and copper acetylacetonate at a concentration of 0.001-1M in a solvent of ethanol, acetylacetone, or DMF.
  • a carrier gas of air or oxygen at a pressure of 25 psi and a flow rate of 3dm 3 /min is supplied and the resulting fine mist is heated to a temperature of 450°C for deposition on a glass substrate.
  • a solution comprising a mixture of yttrium, barium and copper acetates at a concentration of 0.001-1 M is dissolved in water, ethanol, DMF or mixtures thereof.
  • a carrier gas of air or oxygen at a pressure of 25 psi and a flow rate of 3dm 3 /min is supplied and the resulting fine mist is heated to a temperature of 500-1000°C for deposition on an alumina substrate.
  • a mixture of yttrium, barium and copper nitrates at a concentration of 0.001-1M is dissolved in water, ethanol, DMF or mixtures thereof. Air or oxygen at a pressure of 25 psi and a flow rate of 3dm 3 /min is supplied. The resulting mist is heated to a temperature of 500-1000°C and deposited on an alumina substrate.
  • the addition of bismuth or thallium to the superconducting composition YBa 2 Cu 3 O 7-x is known to enhance the desired properties and these elements may be incorporated into the thin coating by the addition of any of the following compounds to the Y-Ba-Cu solution:
  • Bismuth acetate Bi(OOCH 3 ) 3
  • Bismuth nitrate B ⁇ (NO 3 )/5H 2 O
  • Triphenyl bismuth (C 6 H 5 ) 3
  • Bi Bismuth salicylate HOC 6 H 4 CO 2
  • BiO Bismuth alkoxides Bi(RO) 3
  • Bismuth acetylacetonates Bi(CH 3 COCH-COCH 3 ) 3
  • Thallium acetylacetonate Tl(CH 3 COCHCoCH 3 )
  • solution 2 includes an organometallie solute.
  • organometallic derivatives of the following compounds may be any one or more of the organometallic derivatives of the following compounds: a) dithiocarbamic acids S b) dithiocarbimates c) dithiocarbazic acids s d) azodithioformates e) phosphinodithioformates f) dithiocarbonic acids (xanthates) g) trithiocarbonic acids h) dithiomonoselenocarbonic acids
  • the source material is Zn(R-O-CS 2 ) 2 where R is the alky! group C 2 H 5 .
  • the solvent for the source material can be ethanol, DMF or decalin and the concentration of the source material in the solution is in the range of 0.01 to 0.5M.
  • the carrier gas is nitrogen which is supplied at a pressure of 25 psi and a flow rate of 5 dm 3 /min.
  • the growth rate of zinc sulphide on the substrate is greater than 1 ⁇ m/hour with the substrate at a temperature of between 180 to 250°C.
  • the source material is Zn[(C 2 H 5 ) 2 NCSe 2 ] 2 .
  • the solvent for the source material is DMF or a halogenated alkane and the concentration of the source material in the solution is up to 0.5M.
  • the carrier gas is nitrogen which is supplied at a pressure of 20 psi and a flow rate of 3 dm 3 /min.
  • the growth rate of zinc selenide on the substrate is greater than 1 ⁇ m/hour with the substrate at a temperature of between 200 to 300°C.
  • the source material is Ba(S 2 C-OR) 2 .
  • the solvent is DMF and the concentration of the source material in the solution is in the range 0.01 to 0.5M.
  • the carrier gas is nitrogen at a pressure of 25 psi and a flow rate of 3 dm3/min.
  • the growth rate of barium sulphide on the substrate is greater than 1 ⁇ m/hour with the substrate at a temperature of between 250 to 400°C.
  • An advantage of the method and apparatus described above is that by first generating a mist of a solution it is possible to use substances that are either insufficiently volatile or too thermally sensitive for direct vapour generation and transport to the reaction zone.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

On produit un embrun d'une solution (2) d'un mélange de substances contenant les éléments chimiques constitutifs nécessaires dans une couche mince résultante, par exemple en pulvérisant la solution dans une tête de pulvérisation (4) à l'aide d'un gaz porteur. On transporte l'embrun jusqu'à une chambre de réaction chauffée (8) où elle est décomposée, puis on dépose les constituants en couche mince sur un substrat (10). Le substrat peut se présenter sous la forme d'un fil obtenant ainsi un revêtement. Si le gaz porteur est de l'air ou de l'oxygène et si l'on utilise une solution appropriée contenant des composés de Y, Ba et Cu, on peut déposer des couches minces ou des revêtements que l'on peut rendre supraconducteurs. Dans un autre mode de réalisation on peut déposer des couches minces de chalcogénure métallique.
PCT/GB1989/000114 1988-02-09 1989-02-07 Procedes et appareil de depot de couches minces WO1989007667A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888802942A GB8802942D0 (en) 1988-02-09 1988-02-09 Methods & apparatus for depositing thin films
GB8802942 1988-02-09

Publications (1)

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WO1989007667A1 true WO1989007667A1 (fr) 1989-08-24

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WO (1) WO1989007667A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0454843A1 (fr) * 1989-11-21 1991-11-06 Georgia Tech Research Corporation Procede et appareil de deposition rapide en phase vapeur par procede chimique avec des reactifs sous une basse pression de vapeur
US5278138A (en) * 1990-04-16 1994-01-11 Ott Kevin C Aerosol chemical vapor deposition of metal oxide films
US5476547A (en) * 1989-09-26 1995-12-19 Canon Kabushiki Kaisha Gas feeding device for controlled vaporization of an organometallic compound used in deposition film formation
WO1999002756A1 (fr) * 1997-07-14 1999-01-21 Symetrix Corporation Procede et appareil de fabrication de couches minces par depot chimique en phase vapeur
US5888583A (en) * 1988-12-27 1999-03-30 Symetrix Corporation Misted deposition method of fabricating integrated circuits
WO1999029925A1 (fr) * 1997-12-10 1999-06-17 Siemens Aktiengesellschaft Procedes relatifs au o.c.p.v a basse temperature faisant intervenir des bi-carboxylates
US6110531A (en) * 1991-02-25 2000-08-29 Symetrix Corporation Method and apparatus for preparing integrated circuit thin films by chemical vapor deposition
EP1033763A1 (fr) * 1997-09-05 2000-09-06 Matsushita Battery Industrial Co., Ltd. Méthode de formation d'un film mince d'un composé semiconducteur, et cellule solaire utilisant ce film
US6116184A (en) * 1996-05-21 2000-09-12 Symetrix Corporation Method and apparatus for misted liquid source deposition of thin film with reduced mist particle size
EP1134063A1 (fr) * 1998-10-28 2001-09-19 Matsushita Electric Industrial Co., Ltd. Procede de production de couches minces de resine

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1119539A (en) * 1964-10-16 1968-07-10 Philips Electronic Associated Improvements relating to heat-reflecting filters
US3894164A (en) * 1973-03-15 1975-07-08 Rca Corp Chemical vapor deposition of luminescent films
EP0054189A1 (fr) * 1980-12-15 1982-06-23 Hughes Aircraft Company Procédé pour le dépôt photochimique en phase vapeur

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1119539A (en) * 1964-10-16 1968-07-10 Philips Electronic Associated Improvements relating to heat-reflecting filters
US3894164A (en) * 1973-03-15 1975-07-08 Rca Corp Chemical vapor deposition of luminescent films
EP0054189A1 (fr) * 1980-12-15 1982-06-23 Hughes Aircraft Company Procédé pour le dépôt photochimique en phase vapeur

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Journal of the Electrochemical Society, vol. 122, no. 4, April 1975, J.C. Viguie et al.: "Chemical vapor deposition at low temperatures", pages 585-588 *
Thin Solid Films, vol. 128, June 1985, Elsevier Sequoia (Amsterdam, NL), L.F. Zharovsky et al.: "Metal chalco-genide films prepared from chelate organometallic compounds", pages 241-249 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5888583A (en) * 1988-12-27 1999-03-30 Symetrix Corporation Misted deposition method of fabricating integrated circuits
US5476547A (en) * 1989-09-26 1995-12-19 Canon Kabushiki Kaisha Gas feeding device for controlled vaporization of an organometallic compound used in deposition film formation
EP0420596B1 (fr) * 1989-09-26 1996-06-19 Canon Kabushiki Kaisha Dispositif d'alimentation en gaz et appareillage de disposition de films l'employant
US5779804A (en) * 1989-09-26 1998-07-14 Canon Kabushiki Kaisha Gas feeding device for controlled vaporization of an organanometallic compound used in deposition film formation
EP0454843A4 (en) * 1989-11-21 1994-12-28 Georgia Tech Res Inst Method and apparatus for the rapid deposition by chemical vapor deposition with low vapor pressure reactants
EP0454843A1 (fr) * 1989-11-21 1991-11-06 Georgia Tech Research Corporation Procede et appareil de deposition rapide en phase vapeur par procede chimique avec des reactifs sous une basse pression de vapeur
US5278138A (en) * 1990-04-16 1994-01-11 Ott Kevin C Aerosol chemical vapor deposition of metal oxide films
US6110531A (en) * 1991-02-25 2000-08-29 Symetrix Corporation Method and apparatus for preparing integrated circuit thin films by chemical vapor deposition
US6116184A (en) * 1996-05-21 2000-09-12 Symetrix Corporation Method and apparatus for misted liquid source deposition of thin film with reduced mist particle size
US5997642A (en) * 1996-05-21 1999-12-07 Symetrix Corporation Method and apparatus for misted deposition of integrated circuit quality thin films
US6258733B1 (en) 1996-05-21 2001-07-10 Sand Hill Capital Ii, Lp Method and apparatus for misted liquid source deposition of thin film with reduced mist particle size
WO1999002756A1 (fr) * 1997-07-14 1999-01-21 Symetrix Corporation Procede et appareil de fabrication de couches minces par depot chimique en phase vapeur
US6511718B1 (en) 1997-07-14 2003-01-28 Symetrix Corporation Method and apparatus for fabrication of thin films by chemical vapor deposition
EP1033763A1 (fr) * 1997-09-05 2000-09-06 Matsushita Battery Industrial Co., Ltd. Méthode de formation d'un film mince d'un composé semiconducteur, et cellule solaire utilisant ce film
WO1999029925A1 (fr) * 1997-12-10 1999-06-17 Siemens Aktiengesellschaft Procedes relatifs au o.c.p.v a basse temperature faisant intervenir des bi-carboxylates
EP1134063A1 (fr) * 1998-10-28 2001-09-19 Matsushita Electric Industrial Co., Ltd. Procede de production de couches minces de resine
EP1134063A4 (fr) * 1998-10-28 2002-09-18 Matsushita Electric Ind Co Ltd Procede de production de couches minces de resine
US6475571B1 (en) 1998-10-28 2002-11-05 Matsushita Electric Industrial Co., Ltd. Method of producing thin resin films

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