WO2012146828A2 - Process and apparatus for coating - Google Patents

Process and apparatus for coating Download PDF

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Publication number
WO2012146828A2
WO2012146828A2 PCT/FI2012/050412 FI2012050412W WO2012146828A2 WO 2012146828 A2 WO2012146828 A2 WO 2012146828A2 FI 2012050412 W FI2012050412 W FI 2012050412W WO 2012146828 A2 WO2012146828 A2 WO 2012146828A2
Authority
WO
WIPO (PCT)
Prior art keywords
precursor
flow
water
nozzle
substrate
Prior art date
Application number
PCT/FI2012/050412
Other languages
French (fr)
Other versions
WO2012146828A3 (en
Inventor
Joonas Ilmarinen
Original Assignee
Beneq Oy
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 Beneq Oy filed Critical Beneq Oy
Publication of WO2012146828A2 publication Critical patent/WO2012146828A2/en
Publication of WO2012146828A3 publication Critical patent/WO2012146828A3/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • 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
    • C23C16/54—Apparatus specially adapted for continuous coating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1258—Spray pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating

Definitions

  • the present invention relates to a process a process for providing a coating on a substrate and especially to an aerosol-assisted process for providing a coating on a substrate as defined in the preamble of independent claim 1.
  • the present invention further relates to an apparatus for coating a substrate and more particularly to an apparatus for coating a substrate with an aerosol- assisted deposition process as defined in the preamble of independent claim 13. Background of the invention
  • Spray coating is known method for applying a coating on a substrate.
  • an aerosol is formed and deposited on a surface of a substrate.
  • the coating process may be an aerosol -assisted coating process in which at least one of the precursor used for providing the coating is supplied as aerosol particles.
  • the aerosol particles may be liquid droplets or solid particles.
  • Known methods for providing a spray coating by an aerosol- assisted process are described patent publications US 4656963, US 4728353 and US 5540959.
  • a precursor flow is provided by atomizing a liquid precursor into the small droplets and guiding the droplets towards a surface of the substrate.
  • the precursor then reacts on the surface of the substrate to form a coating.
  • the precursor consists of two or more precursor materials which are mixed together with a mixer before atomizing the liquid precursor and supplying to towards the surface of the substrate. Some of the precursor materials are immiscible, thus a solvent have to be used for mixing the precursor materials together.
  • the problem with prior art coating processes is that the mixture of the precursor materials may be highly corrosive.
  • the corrosive precursor causes corrosion of the coating apparatus and its parts.
  • the parts of the apparatus which are subjected to the highly corrosive have to be provided from corrosive resistant materials such as titanium.
  • the corrosive resistant materials are usually expensive and difficult to machine.
  • the use of solvent with the immiscible precursor materials causes cooling of a hot substrate during the coating process. Cooling of the substrate reduces the growth speed of the coating on the substrate.
  • the object of the present invention is to provide a process and apparatus so as to overcome or at least alleviate the prior art disadvantages.
  • the objects of the present invention are achieved with an aerosol-assisted process for providing a coating on a substrate according to the characterizing portion of claim 1.
  • the objects of the present invention are further achieved with an apparatus for coating a substrate with an aerosol-assisted deposition process according to the characterizing portion of claim 13.
  • An aerosol-assisted coating deposition process may be a pyrolytic coating deposition process, such as an aerosol-assisted chemical vapor deposition (AACVD) process or a spray pyrolysis processes, but other deposition processes where aerosols are applied are within the scope of this invention.
  • An aerosol is a mixture of at least one gas component and particles, in this case liquid particles, or droplets, or solid particles.
  • the aerosol assisted coating refers to a coating process in which at least one of the precursor materials is supplied as liquid droplets or solid particles.
  • the present invention is based on the idea of providing an aerosol-assisted process for providing a coating on a substrate in which process precursors react on a surface of the substrate for providing the coating.
  • the process of the present invention comprises providing a first precursor flow and supplying the first precursor into a reaction space for subjecting the substrate to the first precursor flow in the reaction space, the first precursor flow comprising at least one first precursor material for providing the coating , and providing a second precursor flow and supplying the second precursor flow into the reaction space for subjecting the substrate to the second precursor flow in the reaction space, the second precursor flow being separate from the first precursor flow, the second precursor flow comprising at least one second precursor material .
  • the present invention further comprises providing a water flow, the water flow being separate from the first precursor flow and the second precursor flow and supplying the water flow into the reaction space for accelerating the surface reactions providing the coating.
  • the water flow may supplied into the reaction space separately from the first and second precursor flows and mixed to the first or second precursor flow in the reaction space, or the water flow may be mixed to the first or second precursor flow at an inlet of the reaction space during supplying the second precursor flow into the reaction space, or the water flow may be mixed to the first or second precursor flow upstream of the reaction space or in the reaction space.
  • the water flow and the first or second precursor flow may be mixed in the reaction space before the first or second precursor reacts on the surface of the substrate.
  • the present invention relates to subjecting the substrate to a first precursor flow, the first precursor flow comprising at least one first precursor material for providing the coating.
  • the present invention further comprises subjecting the substrate to a second precursor flow, the second precursor flow being separate from the first precursor flow, and the second precursor flow comprising at least one second precursor material .
  • water flow is further added or mixed to the second precursor flow before or during the second precursor is supplied to the reaction space or in the reaction space such that the second precursor flow comprises a mixture of the second precursor and water.
  • Water or water vapor may be used in aerosol-assisted deposition processes for accelerating the surface reactions of the precursors.
  • the process of the present invention may be carried out with a n apparatus for coating a substrate with an aerosol -assisted deposition process in which process precursor materials react on a surface of the substrate for providing a coating on the substrate.
  • the apparatus comprises at least one first precursor nozzle for providing a first precursor flow, the first precursor flow comprising at least one first precursor material for providing the coating, and at least one second precursor nozzle for providing a second precursor flow, the second precursor flow comprising at least one second precursor material for providing the coating, the second precursor nozzle being arranged to supply the second precursor flow separately from the first precursor flow .
  • the apparatus is further arranged to add or mix water to the second precursor flow before or during supplying the second precursor to the deposition chamber or in a deposition chamber such that the second precursor flow comprises a mixture of at least one second precursor material and water.
  • the second precursor nozzle may thus supply both the second precursor and the water or the second precursor nozzle may be arranged to mix the second precursor flow and the water flow during supplying or to supply the second precursor flow and the water flow separately to the deposition chamber such that they are mixed in the deposition chamber.
  • the apparatus comprises a water nozzle for supplying the water flow to the deposition chamber separately from the second precursor flow.
  • the present invention provides a process and apparatus for coating a substrate with an aerosol-assisted deposition method.
  • at least one of the precursors is supplied to the coating zone or deposition chamber as an aerosol comprising liquid droplets or solid particles.
  • the precursors are supplied from at least two different precursor sources and as at least two different precursor flows.
  • the different precursor flows are kept separated from each other such that the precursor materials are mixed after they supplied to a deposition zone or deposition chamber, the reaction space.
  • the different precursor flows may be mixed together before they react on the surface of the substrate or they may react together on the surface of the substrate to form a coating.
  • water flow id added or mixed to at least one of the separated precursor flows before or during supplying the at least one of the separated precursor flows or in the reaction space.
  • one of the separately supplied precursor flows is supplied towards the surface of the substrate with a water flow.
  • the advantage of the present invention is that when two or more different precursor materials are supplied as separate precursor flows and the water flow is mixed to one of the precursors flows before the precursor reacts on the surface of the substrate, there is no need to provide a corrosive mixture of the precursor materials before they are supplied to the coating zone.
  • the corrosive mixture of the precursor materials is provided only in the coating zone or on the surface of the substrate. This may also reduce need for maintenance or lengthen the maintenance interval. Therefore, there is no need to manufacture the parts of the coating apparatus from corrosive resistant materials upstream of the coating zone.
  • adding or mixing water flow to the at least one of the precursor materials enables the process to be carried out with out adding solvent, such as methanol, to the precursor mixture. In some embodiments also mixing means for proving a precursor mixture before supplying it may be avoided.
  • Figure 1 shows one embodiment an apparatus of the present invention for providing a coating with aerosol-assisted deposition
  • Figure 2 shows one embodiment of an atomizer to be used in apparatus of figure 1;
  • FIGS. 3 to 9 show different embodiments of an apparatus of the present invention for providing a coating with aerosol-assisted deposition. Detailed description of the invention
  • the figure 1 shows one apparatus 3 according to the present invention for coating a substrate 1 with an aerosol-assisted deposition method.
  • the apparatus 3 comprises deposition chamber, or reaction space, 5 in which the coating reactions are carried for providing a coating 2 on the substrate 1.
  • the apparatus 3 is further provided with an exhaust conduit 12 for discharging gases, precursors not reacted on the surface of the substrate, additional reaction products or some other gaseous or aerosol materials from the deposition chamber 5.
  • the deposition chamber 5 is isolated from the ambient atmosphere with gas curtains provided by the gas curtain nozzles 4.
  • the substrate 1 may be transported to or through or from below the deposition chamber 5 with conveyor means 32 in a moving direction .
  • the conveyor means 32 comprise transport rollers for transporting the substrate 1.
  • the substrate 1 may be material web, such as flat glass, or separate object, such as thin silicon substrate.
  • the substrate 1 may be for example glass, metal or ceramic substrate.
  • the precursor forming the coating 2 on the substrate 1 consists of two or more precursor materials taking part to the surface reactions and formation of the coating 2.
  • the precursor forming the coating is divided to at least first precursor and the second precursor.
  • the first and second precursor may comprise one or more precursor materials for forming the coating 2.
  • the first precursor comprises at least one precursor material different from the precursor materials present in the second precursor.
  • two or more separate precursor flows are provided.
  • a first precursor flow is provided from the first precursor and a second precursor flow is provided from the second precursor. Therefore, the second precursor flow comprises at least one precursor material not present in the first precursor flow or the first precursor flow comprises at least one precursor material not present in the first precursor flow. It should be noted that the precursor may also be divided into three or more separate precursor flows. Each of the precursor flows comprising at least one precursor material not present in the other precursor flows, or at least one of the precursor flows comprising at least one precursor material not present in the other precursor flows.
  • the coating apparatus 3 further comprises a first precursor nozzle 7 arranged to supply a first precursor into the deposition chamber, or reaction space, 5.
  • the first precursor may consist of one or more precursor materials.
  • the first precursor is a liquid precursor and the first precursor nozzle 7 is arranged to atomize the first precursor into droplets 8 and to guide the droplets 8 towards a surface 34 of the substrate 1.
  • the first precursor nozzle 7 may comprise a two fluid atomizer arranged to produce droplets 8 with an atomizing gas.
  • the produced droplets may have preferably a diameter less than 10 micrometers and more preferably less than 3 micrometers.
  • the droplets 8 and the gas used for atomizing the first precursor essentially do not contain precursor materials for producing the coating 2.
  • the apparatus 3 further comprises a first conduit 6 for transporting the first precursor flow from the first precursor nozzle to the deposition chamber 5 or towards the surface 34 of the substrate 1.
  • the first precursor nozzle 6 is arranged to the first conduit 6.
  • the first precursor conduit 6 may thus form a first atomization chamber which is in fluid communication with the deposition chamber 5 for conducting the first precursor flow to the deposition chamber 5.
  • the first precursor conduit 6 may thus form part of the deposition chamber or reaction space 5.
  • Figure 2 shows one embodiment of the atomizer of the first precursor nozzle 7 for producing droplets 8 having diameter less than 10 micrometers.
  • the atomizer comprises precursor channel 44 for supplying liquid precursor to atomization head 45.
  • the atomizer further comprises an atomizing gas channel 46 for supplying atomizing gas to the atomizer.
  • a pressure chamber 47 is used to provide uniform gas flow through atomizing gas supply channel 48.
  • On the atomizing head 45 of the precursor channel 45 the atomizing gas flow atomizes the liquid precursor into primary droplets.
  • the atomizer further comprises an atomizing chamber 49 provided with chokes 50 extending from the inner wall of the atomizing chamber 49.
  • the chokes 50 are arranged for changing the hydrodynamic properties of the aerosol flow discharging from the atomizing head 45 in a manner reducing the droplet size of the aerosol before it is conducted onto the surface of the glass, wherein the flow restraints are arranged in such a manner that the average aerodynamic diameter of the droplets of the aerosol discharging from the atomizer is, 10 micrometers, preferably 3 micrometres or less, more preferably 1 micrometre or less.
  • a second precursor nozzle 10 is arranged to the apparatus 3.
  • the second precursor nozzle 10 is arranged to provide a second precursor flow of second precursor.
  • the second precursor nozzle 10 is arranged to supply second precursor into the deposition chamber 5.
  • the second precursor nozzle is provided as a gas nozzle arranged to supply gaseous second precursor flow into the deposition chamber 5 for providing the coating 2 on the substrate 1.
  • the first precursor is liquid precursor and the first precursor is atomized into droplets 8 for providing the first precursor flow comprising droplets 8 and the second precursor is a gaseous precursor and the second precursor flow is gaseous precursor flow.
  • the second precursor nozzle 10 is arranged inside the deposition chamber 5.
  • the deposition chamber 5 is provided with a throttle 30 for equalizing the first precursor flow in the deposition chamber 5.
  • the throttle 30 is arranged downstream of the first precursor nozzle 7 in the moving direction of the substrate 1.
  • the second precursor nozzle 10 is arranged downstream of the throttle 30 in the moving direction of the substrate 1.
  • the apparatus may further comprise heaters or heating means for providing thermal energy to the deposition chamber such that the liquid precursor droplets may be vaporized before they collide on the surface 34 of the substrate 1.
  • the substrate 1 itself may be have or provided with the thermal energy for vaporizing the liquid droplets before they collide on the surface 34, or the heaters may heat the substrate 1 to a required temperature for vaporizing the droplets.
  • the second precursor nozzle is arranged to supply water vapor together with the gaseous second precursor.
  • the second precursor nozzle 10 is arranged to supply the second precursor flow and the water vapor flow separately to the deposition chamber 5 such that the water vapor flow and the second precursor flow are mixed together in the deposition chamber 5 before the second precursor reacts on the surface 34 of the substrate 1.
  • the apparatus of figure 1 may comprise a mixer for mixing the second precursor flow and the water vapor flow together before the second precursor nozzle 10.
  • Figure 1 shows a first precursor supply line 23 through which a first precursor flow is supplied to the first precursor nozzle 7 from a first precursor source (not shown), a second precursor supply line 21 through which the second precursor flow is supplied from a second precursor source (not shown) to the second precursor nozzle 10 and a water supply line 22 through which flow or water vapor flow is supplied from a water source (not shown) to the second precursor nozzle 10.
  • the second precursor supply line 21 and the water supply line 22 are connected to each other upstream of the second precursor nozzle 10 for mixing the water flow and the second precursor flow before supplying them to the deposition chamber 5.
  • the water flow and the precursor flow are mixed in the vicinity of the second precursor nozzle 10.
  • the mixer may be arranged to mix the water flow and the second precursor flow together prior the second precursor nozzle 10.
  • the second precursor nozzle 10 may be arranged to mix water vapor flow and the second precursor flow together during supplying the second precursor flow from the second precursor nozzle 10. Therefore second precursor nozzle 10 may be provided to supply the second precursor and the water vapor from different sources such that the water vapor and the second precursor are mixed during or after supplying them from the second precursor nozzle 10. This means that the second precursor flow and the water vapor flow are mixed before the second precursor or the precursors react on the surface 34 of the substrate 1.
  • the second precursor nozzle may be arranged to mix liquid water flow to the gaseous second precursor flow during the supply, or alternative the second precursor flow may be arranged to atomize liquid water flow to water droplets and supply the water droplets to the deposition chamber 5 together with the second precursor flow or separately from the second precursor flow such that the water droplets flow and the gaseous second precursor flow are mixed together in the deposition chamber 5.
  • the first and second precursor source and the water source are separate sources and they may be or comprise a container, a liquid container, a gas container or the like.
  • Figure 3 shows another embodiment of an apparatus according to the present invention.
  • the apparatus of figure 3 comprises substantially the same components as the apparatus of figure 1.
  • the apparatus comprises a second precursor nozzle 10 and a separate water nozzle 11.
  • the first precursor supply line 23 supplies first precursor separately to the first precursor nozzle 7
  • the second precursor supply line 21 supplies second precursor separately to the second precursor nozzle 10
  • the water supply line 22 supplies water to the water nozzle 11.
  • the second precursor nozzle 10 is provided as gas nozzle for supplying second gaseous precursor into the deposition chamber 5.
  • the water nozzle 11 of figure 3 is arranged to supply water vapor into the deposition chamber 5. Accordingly, the water nozzle 11 and the second precursor nozzle 10 are arranged such that the water flow and the second precursor flow are mixed together in the deposition chamber 5, or reaction space, before the second precursor react on the surface 34 of the substrate 1.
  • the terms water flow and precursor flow mean the material flow from a water source or precursor source until the water or precursor reach the surface of the substrate in the deposition chamber 5 or until the water or precursor takes part in the surface reactions on the surface 34 of the substrate 1.
  • both the second precursor nozzle 10 and the water nozzle are located inside the deposition chamber 5. Furthermore, the second precursor nozzle 10 is arranged downstream of the first precursor nozzle 7 in the moving direction of the substrate 1. Also the water nozzle 11 is arranged downstream of the first precursor nozzle 7 in the moving direction of the substrate 1. The second precursor nozzle 10 is arranged downstream of the water nozzle 11, but in another embodiment they may be arranged oppositely. The second precursor nozzle 10 and the water nozzle 11 are arranged downstream of the throttle 30 in the moving direction of the substrate 1.
  • Figure 4 shows another embodiment of the present invention, in which the first precursor is liquid precursor and the first precu rsor is atomized into droplets 8 for providing the first precursor flow comprising droplets 8 and the second precursor is liquid precursor and the second precursor is atomized into droplets 13 for providing the second precursor flow comprising droplets 13.
  • the first precursor nozzle 7 comprises an atomizer for atomizing the first liquid precursor into dropl ets 8 and the second precursor nozzle 10 comprises an atomizer for atomizing the second liquid precursor into droplets 13.
  • the first and second precursor nozzle 7, 10 are preferably arranged to produce droplets 8, 13 having the average aerodynamic diameter less than 10 micrometers, preferably 3 micrometres or less, more preferably 1 micrometre or less.
  • the atomizer of figure 2 may be used for producing the droplets 8, 13.
  • the apparatus 3 further comprises a second conduit 9 for transporting the second precursor flow from the second precursor nozzle 10 to the deposition chamber 5 or towards the surface 34 of the substrate 1.
  • the second precursor nozzle 10 is arranged to the second conduit 9.
  • the second precursor conduit 9 may thus form a second atomization chamber which is in fluid communication with the deposition chamber 5 for conducting the first precursor flow to the deposition chamber 5.
  • the second precursor conduit 9 may thus form part of the deposition chamber or reaction space 5.
  • the apparatus is further arranged to mix water flow to the second precursor flow.
  • the water flow may be mixed to the liquid second precursor flow before, during or after supplying the second precursor from the second precursor nozzle 10 to the deposition chamber 5.
  • Figure 4 shows an embodiment in which the second precursor nozzle 10 may be arranged to supply water flow and second precursor flow from different sources such that second precursor flow and the water flow are mixed during or after atomization in the second precursor nozzle 10.
  • the second precursor is supplied to the second precursor nozzle 10 via the second precursor supply line 21 and the water flow is supplied to the second precursor nozzle 10 via water supply line 22 separately from the second precursor flow.
  • the water may be supplied as water vapour flow or as liquid water flow which is atomized into water droplets.
  • the second precursor nozzle 10 may arranged to supply both second precursor flow and water flow separately to the deposition chamber 5 such that the second precursor flow and the water flow are mixed in the deposition chamber 5.
  • the at least one second precursor nozzle 10 is arranged to mix the second precursor flow and water flow together and supply the mixture to the deposition chamber 5.
  • the water flow and the second precursor flow may be mixed before or upstream of the second precursor nozzle 10 such that the second precursor nozzle 10 atomizes the mixture of the second precursor flow and water flow into droplets 13 for supplying second precursor flow comprising water and second precursor to the deposition chamber 5, as shown in connection with figure 1.
  • the second precursor nozzle 10 is arranged downstream of the first precursor nozzle 7.
  • the second precursor nozzle 10 may be further arranged downstream of the throttle 30 in the moving direction of the substrate 1.
  • the apparatus further comprises charging means for electrically charging the droplets 8.
  • the charging means may also be arranged to charge both the first precursor droplets 8 and second precursor 13, or only droplets 13.
  • the charging means are arranged to electrically charge the droplets 8 by a charger 101 and an electric field created between electrode 103 and coelectrode 104 is used to guide droplets 8 towards to the surface 34 of substrate 1.
  • the charger 101 is a corona charger and the required high voltage is supplied from a high voltage generator 102.
  • Figure 5 shows another embodiment of the apparatus 3 according to the present invention.
  • the first precursor is liquid precursor and the first precursor is atomized into droplets 8 for providing the first precursor flow comprising droplets 8 and the second precursor is liquid precursor and the second precursor is atomized into droplets 8 for providing the second precursor flow comprising droplets 13.
  • the embodiment of figure 5 corresponds the apparatus of figure 4, except that the there is a separate water nozzle 11 arranged to the second conduit.
  • the first precursor supply line 23 supplies first precursor separately to the first precursor nozzle 7, the second precursor supply line 21 supplies second precursor separately to the second precursor nozzle 10, and the water supply line 22 supplies water to the water nozzle 11.
  • liquid water is supplied from the water nozzle 11 for providing a water flow into the deposition chamber 5.
  • the second precursor nozzle 10 and the water nozzle 11 are arranged such that the second precursor flow and the water flow are mixed in the second conduit 9 or further in the deposition chamber 5, or reaction space.
  • the water flow and the second precursor flow may be supplied towards the surface 34 of the substrate such that they mix together before the surface 34 of the substrate, preferably in the second conduit 9.
  • the water nozzle 11 may comprise an atomizer for atomizing liquid form water into water droplets for providing a water flow comprising water droplets .
  • the water nozzle 11 may also be arranged to supply water vapor, thus it may be a gas nozzle.
  • Figure 6 shows yet another embodiment of the present invention, in which the first precursor is liquid precursor and the first precu rsor is atomized into droplets 8 for providing the first precursor flow comprising droplets 8 and the second precursor is liquid precursor and the second precursor is atomized into droplets 13 for providing the second precursor flow comprising droplets 13.
  • the first precursor nozzle 7 comprises an atomizer for atomizing the first liquid precursor into dropl ets 8 and the second precursor nozzle 10 comprises an atomizer for atomizing the second liquid precursor into droplets 13.
  • the apparatus 3 is further provided with a separate water nozzle 11 arranged to supply water vapor into the deposition chamber 5.
  • the first precursor supply line 23 supplies first precursor separately to the first precursor nozzle 7
  • the second precursor supply line 21 supplies second precursor separately to the second precursor nozzle 10
  • the water supply line 22 supplies water separately to the water nozzle 11.
  • the water nozzle 11 and the second precursor nozzle 10 are arranged such that the water vapor flow and the second precursor flow are mixed in the deposition chamber 5.
  • the water nozzle 11 is arranged downstream of the first precursor nozzle 7 in the moving direction of the substrate 1.
  • the second precursor nozzle 10 is further arranged downstream of the water nozzle 11.
  • the second precursor nozzle 10 and the water nozzle 11 are arranged downstream of the throttle 30 in the moving direction of the substrate 1.
  • Figure 7 shows another embodiment of the present invention, in which the first precursor is liquid precursor and the first precursor is atomized into droplets 8 for providing the first precursor flow comprising droplets 8 and the second precursor is liquid precursor and the second precursor is atomized into droplets 13 for providing the second precursor flow comprising droplets 13.
  • the first and second precursor nozzle 7, 10 are arranged to atomize and supply the first and precursors to the same the first conduit 6, which may be an atomization chamber. Therefore, the first precursor nozzle 7 comprises an atomizer for atomizing the first liquid precursor into droplets 8 and the second precursor nozzle 10 comprises an atomizer for atomizing the second liquid precursor into droplets 13.
  • the apparatus 3 is further provided with a separate water nozzle 11 arranged to supply water vapor into the deposition chamber 5.
  • the first precursor supply line 23 supplies first precursor separately to the first precursor nozzle 7, the second precursor supply line 21 supplies second precursor separately to the second precursor nozzle 10, and the water supply line 22 supplies water separately to the water nozzle 11.
  • the first precursor nozzle 7 and the second precursor nozzle 10 are arranged such that the first and second precursor flows are mixed in the deposition chamber 5.
  • the water nozzle 11 is arranged downstream of the first and second precursor nozzle 7, 10 in the moving direction of the substrate 1 such that the water or water vapor is mixed to the mixture of the first and second precursor flows.
  • the water nozzle 11 is arranged downstream of the throttle 30 in the moving direction of the substrate 1.
  • Figure 8 shows an alternative embodiment in which the second precursor nozzle 10 and the water nozzle have changed places in relation to the embodiment of figure 7.
  • Figure 9 further shows an embodiment in which water supply line 22 is connected to the second precursor supply line 21 for supplying water and second precursor into the deposition chamber 5 via the second precursor nozzle 10.
  • the apparatus of the present invention comprise a deposition chamber first precursor supply means 7, 23 for providing a first precursor flow, the first precursor flow comprising at least one first precursor material for providing the coating and second precursor supply means 10, 21 for providing a second precursor flow, the second precursor flow comprising at least one second precursor material for providing the coating, the second precursor nozzle being arranged to supply the second precursor flow sepa rately from the first precursor flow.
  • the apparatus may also comprise a mixing chamber (not shown) for mixing the first and second precursor flow before the precursors react on the surface 34 of the substrate 1. The mixing chamber forms part of the deposition chamber 5.
  • the mixing chamber may also alternatively be arranged for mixing the second precursor flow and the water flow together before the precursors react on the surface 34 of the substrate 1, or the first and second precursor flow and the water flow.
  • the first precursor may be a gaseous precursor
  • the first precursor nozzle 7 comprises a gas nozzle for providing the first gaseous precursor flow.
  • TCO transparent conductive oxide
  • TCO coatings fluorine doped tin oxide (FTO) coating provided from an organic compound of tin, such as monobutyltin trichloride (MBTC) and a tin-doping fluorine source, such as hydrogen fluorine (HF) or an organic source, such as trifluoroacetic acid (TFA, C2H F3O2) .
  • FTO fluorine doped tin oxide
  • MBTC monobutyltin trichloride
  • a tin-doping fluorine source such as hydrogen fluorine (HF) or an organic source, such as trifluoroacetic acid (TFA, C2H F3O2) .
  • MBTC and TFA cannot be mixed together without an additional solvent, which usually comprises oxygen, such as methyl alcohol (CH3OH) .
  • an additional solvent which usually comprises oxygen, such as methyl alcohol (CH3OH) .
  • the process and apparatus described in the present invention allows using MBTC as the first precursor and TFA as the second precursor.
  • MBTC and TFA are supplied separately to the deposition chamber 5 and furthermore TFA is supplied together with a water to the deposition chamber 5.
  • Water radically increases the coating growth rate of FTO coatings.
  • the FTO coating is formed on glass substrates at relatively low temperatures (below 650°C)
  • it is preferred to supply water in vapor form because evaporating the water droplets is energy-consuming and would thus cool down the surface of the glass substrate, which is unfavorable to the coating growth.
  • the mixture of MBTC and TFA is highly corrosive and the in the present invention they are mixed at the deposition chamber, not in the supply means.
  • a first precursor flow is supplied towards the surface 34 of the substrate 1 and a second precursor flow is supplied towards the surface 34 of the substrate 1 separately from the first precursor flow.
  • Water flow is added or mixed to the second precursor flow in the deposition chamber 5 or before or during the supply from the second precursor nozzle 10 before the second precursor reacts on the surface 34 of the substrate 1.
  • the apparatus and process may be arranged to first subjecting the surface 34 of the substrate 1 to the first precursor flow and then to the second precursor flow or the second precursor flow and the water flow, or mixing the first and second precursor flow before the precursors react on the surface 34 of the substrate 1, or mixing the first precursor flow, second precursor flow and the water flow together before the precursors react on the surface 34 of the substrate 1 .
  • water may be supplied to the deposition chamber as liquid form or as vapor.
  • the first and/or second are supplied to the to the deposition chamber as liquid form or as vapor, such that at least one of them is supplied as liquid droplets or solid particles.

Abstract

The present invention relates to an aerosol-assisted process for providing a coating (2) on a substrate (1) in which process precursors react on a surface (34) of the substrate (1) for providing the coating (2). The process comprises providing a first precursor flow and a second precursor flow separate from the first precursor flow. The process further comprises providing a water flow, the water flow being separate from the first precursor flow and the second precursor flow and supplying the water flow into the reaction space (5) for accelerating the surface reactions providing the coating (2).

Description

Process and apparatus for coating Field of the invention
The present invention relates to a process a process for providing a coating on a substrate and especially to an aerosol-assisted process for providing a coating on a substrate as defined in the preamble of independent claim 1. The present invention further relates to an apparatus for coating a substrate and more particularly to an apparatus for coating a substrate with an aerosol- assisted deposition process as defined in the preamble of independent claim 13. Background of the invention
Spray coating is known method for applying a coating on a substrate. In spay coating an aerosol is formed and deposited on a surface of a substrate. The coating process may be an aerosol -assisted coating process in which at least one of the precursor used for providing the coating is supplied as aerosol particles. The aerosol particles may be liquid droplets or solid particles. Known methods for providing a spray coating by an aerosol- assisted process are described patent publications US 4656963, US 4728353 and US 5540959.
In the prior art aerosol-assisted coating process a precursor flow is provided by atomizing a liquid precursor into the small droplets and guiding the droplets towards a surface of the substrate. The precursor then reacts on the surface of the substrate to form a coating. In many cases the precursor consists of two or more precursor materials which are mixed together with a mixer before atomizing the liquid precursor and supplying to towards the surface of the substrate. Some of the precursor materials are immiscible, thus a solvent have to be used for mixing the precursor materials together.
The problem with prior art coating processes is that the mixture of the precursor materials may be highly corrosive. The corrosive precursor causes corrosion of the coating apparatus and its parts. The parts of the apparatus which are subjected to the highly corrosive have to be provided from corrosive resistant materials such as titanium. The corrosive resistant materials are usually expensive and difficult to machine. Furthermore, the use of solvent with the immiscible precursor materials causes cooling of a hot substrate during the coating process. Cooling of the substrate reduces the growth speed of the coating on the substrate.
Brief description of the invention
The object of the present invention is to provide a process and apparatus so as to overcome or at least alleviate the prior art disadvantages. The objects of the present invention are achieved with an aerosol-assisted process for providing a coating on a substrate according to the characterizing portion of claim 1. The objects of the present invention are further achieved with an apparatus for coating a substrate with an aerosol-assisted deposition process according to the characterizing portion of claim 13.
The preferred embodiments of the invention are disclosed in the dependent claims.
An aerosol-assisted coating deposition process may be a pyrolytic coating deposition process, such as an aerosol-assisted chemical vapor deposition (AACVD) process or a spray pyrolysis processes, but other deposition processes where aerosols are applied are within the scope of this invention. An aerosol is a mixture of at least one gas component and particles, in this case liquid particles, or droplets, or solid particles. In the present invention the aerosol assisted coating refers to a coating process in which at least one of the precursor materials is supplied as liquid droplets or solid particles.
The present invention is based on the idea of providing an aerosol-assisted process for providing a coating on a substrate in which process precursors react on a surface of the substrate for providing the coating. The process of the present invention comprises providing a first precursor flow and supplying the first precursor into a reaction space for subjecting the substrate to the first precursor flow in the reaction space, the first precursor flow comprising at least one first precursor material for providing the coating , and providing a second precursor flow and supplying the second precursor flow into the reaction space for subjecting the substrate to the second precursor flow in the reaction space, the second precursor flow being separate from the first precursor flow, the second precursor flow comprising at least one second precursor material . The present invention further comprises providing a water flow, the water flow being separate from the first precursor flow and the second precursor flow and supplying the water flow into the reaction space for accelerating the surface reactions providing the coating. In the present invention the water flow may supplied into the reaction space separately from the first and second precursor flows and mixed to the first or second precursor flow in the reaction space, or the water flow may be mixed to the first or second precursor flow at an inlet of the reaction space during supplying the second precursor flow into the reaction space, or the water flow may be mixed to the first or second precursor flow upstream of the reaction space or in the reaction space. In one embodiment the water flow and the first or second precursor flow may be mixed in the reaction space before the first or second precursor reacts on the surface of the substrate.
Accordingly the present invention relates to subjecting the substrate to a first precursor flow, the first precursor flow comprising at least one first precursor material for providing the coating. The present invention further comprises subjecting the substrate to a second precursor flow, the second precursor flow being separate from the first precursor flow, and the second precursor flow comprising at least one second precursor material . In the process water flow is further added or mixed to the second precursor flow before or during the second precursor is supplied to the reaction space or in the reaction space such that the second precursor flow comprises a mixture of the second precursor and water. Water or water vapor may be used in aerosol-assisted deposition processes for accelerating the surface reactions of the precursors.
The process of the present invention may be carried out with a n apparatus for coating a substrate with an aerosol -assisted deposition process in which process precursor materials react on a surface of the substrate for providing a coating on the substrate. The apparatus comprises at least one first precursor nozzle for providing a first precursor flow, the first precursor flow comprising at least one first precursor material for providing the coating, and at least one second precursor nozzle for providing a second precursor flow, the second precursor flow comprising at least one second precursor material for providing the coating, the second precursor nozzle being arranged to supply the second precursor flow separately from the first precursor flow . The apparatus is further arranged to add or mix water to the second precursor flow before or during supplying the second precursor to the deposition chamber or in a deposition chamber such that the second precursor flow comprises a mixture of at least one second precursor material and water. The second precursor nozzle may thus supply both the second precursor and the water or the second precursor nozzle may be arranged to mix the second precursor flow and the water flow during supplying or to supply the second precursor flow and the water flow separately to the deposition chamber such that they are mixed in the deposition chamber. Alternatively the apparatus comprises a water nozzle for supplying the water flow to the deposition chamber separately from the second precursor flow.
According to the above mentioned present invention provides a process and apparatus for coating a substrate with an aerosol-assisted deposition method. In the present invention at least one of the precursors is supplied to the coating zone or deposition chamber as an aerosol comprising liquid droplets or solid particles. In the present invention the precursors are supplied from at least two different precursor sources and as at least two different precursor flows. The different precursor flows are kept separated from each other such that the precursor materials are mixed after they supplied to a deposition zone or deposition chamber, the reaction space. The different precursor flows may be mixed together before they react on the surface of the substrate or they may react together on the surface of the substrate to form a coating. According to the invention water flow id added or mixed to at least one of the separated precursor flows before or during supplying the at least one of the separated precursor flows or in the reaction space. In other words one of the separately supplied precursor flows is supplied towards the surface of the substrate with a water flow.
The advantage of the present invention is that when two or more different precursor materials are supplied as separate precursor flows and the water flow is mixed to one of the precursors flows before the precursor reacts on the surface of the substrate, there is no need to provide a corrosive mixture of the precursor materials before they are supplied to the coating zone. The corrosive mixture of the precursor materials is provided only in the coating zone or on the surface of the substrate. This may also reduce need for maintenance or lengthen the maintenance interval. Therefore, there is no need to manufacture the parts of the coating apparatus from corrosive resistant materials upstream of the coating zone. Furthermore, adding or mixing water flow to the at least one of the precursor materials enables the process to be carried out with out adding solvent, such as methanol, to the precursor mixture. In some embodiments also mixing means for proving a precursor mixture before supplying it may be avoided. Brief description of the figures
In the following the invention will be described in greater detail, in connection with preferred embodiments, with reference to the attached drawings, in which
Figure 1 shows one embodiment an apparatus of the present invention for providing a coating with aerosol-assisted deposition; Figure 2 shows one embodiment of an atomizer to be used in apparatus of figure 1; and
Figures 3 to 9 show different embodiments of an apparatus of the present invention for providing a coating with aerosol-assisted deposition. Detailed description of the invention
The figure 1 shows one apparatus 3 according to the present invention for coating a substrate 1 with an aerosol-assisted deposition method. It should be noted that same reference numerals are used to denote same or corresponding parts or features in all figures 1 to 9. The apparatus 3 comprises deposition chamber, or reaction space, 5 in which the coating reactions are carried for providing a coating 2 on the substrate 1. The apparatus 3 is further provided with an exhaust conduit 12 for discharging gases, precursors not reacted on the surface of the substrate, additional reaction products or some other gaseous or aerosol materials from the deposition chamber 5. The deposition chamber 5 is isolated from the ambient atmosphere with gas curtains provided by the gas curtain nozzles 4. The substrate 1 may be transported to or through or from below the deposition chamber 5 with conveyor means 32 in a moving direction . In figures 1 to 6 the conveyor means 32 comprise transport rollers for transporting the substrate 1. However, it should be noted that the conveyor means may be any other means suitable for transporting the substrate 1. The substrate 1 may be material web, such as flat glass, or separate object, such as thin silicon substrate. The substrate 1 may be for example glass, metal or ceramic substrate. In the present invention the precursor forming the coating 2 on the substrate 1 consists of two or more precursor materials taking part to the surface reactions and formation of the coating 2. In the present invention the precursor forming the coating is divided to at least first precursor and the second precursor. The first and second precursor may comprise one or more precursor materials for forming the coating 2. In the present invention the first precursor comprises at least one precursor material different from the precursor materials present in the second precursor. Thus in the present invention two or more separate precursor flows are provided. In other words a first precursor flow is provided from the first precursor and a second precursor flow is provided from the second precursor. Therefore, the second precursor flow comprises at least one precursor material not present in the first precursor flow or the first precursor flow comprises at least one precursor material not present in the first precursor flow. It should be noted that the precursor may also be divided into three or more separate precursor flows. Each of the precursor flows comprising at least one precursor material not present in the other precursor flows, or at least one of the precursor flows comprising at least one precursor material not present in the other precursor flows.
The coating apparatus 3 further comprises a first precursor nozzle 7 arranged to supply a first precursor into the deposition chamber, or reaction space, 5. The first precursor may consist of one or more precursor materials. The first precursor is a liquid precursor and the first precursor nozzle 7 is arranged to atomize the first precursor into droplets 8 and to guide the droplets 8 towards a surface 34 of the substrate 1. The first precursor nozzle 7 may comprise a two fluid atomizer arranged to produce droplets 8 with an atomizing gas. The produced droplets may have preferably a diameter less than 10 micrometers and more preferably less than 3 micrometers. The droplets 8 and the gas used for atomizing the first precursor essentially do not contain precursor materials for producing the coating 2. The apparatus 3 further comprises a first conduit 6 for transporting the first precursor flow from the first precursor nozzle to the deposition chamber 5 or towards the surface 34 of the substrate 1. As shown in figure 1, the first precursor nozzle 6 is arranged to the first conduit 6. The first precursor conduit 6 may thus form a first atomization chamber which is in fluid communication with the deposition chamber 5 for conducting the first precursor flow to the deposition chamber 5. The first precursor conduit 6 may thus form part of the deposition chamber or reaction space 5.
Figure 2 shows one embodiment of the atomizer of the first precursor nozzle 7 for producing droplets 8 having diameter less than 10 micrometers. The atomizer comprises precursor channel 44 for supplying liquid precursor to atomization head 45. The atomizer further comprises an atomizing gas channel 46 for supplying atomizing gas to the atomizer. A pressure chamber 47 is used to provide uniform gas flow through atomizing gas supply channel 48. On the atomizing head 45 of the precursor channel 45 the atomizing gas flow atomizes the liquid precursor into primary droplets. The atomizer further comprises an atomizing chamber 49 provided with chokes 50 extending from the inner wall of the atomizing chamber 49. Thus the chokes 50 are arranged for changing the hydrodynamic properties of the aerosol flow discharging from the atomizing head 45 in a manner reducing the droplet size of the aerosol before it is conducted onto the surface of the glass, wherein the flow restraints are arranged in such a manner that the average aerodynamic diameter of the droplets of the aerosol discharging from the atomizer is, 10 micrometers, preferably 3 micrometres or less, more preferably 1 micrometre or less. As shown in figure 1, a second precursor nozzle 10 is arranged to the apparatus 3. The second precursor nozzle 10 is arranged to provide a second precursor flow of second precursor. In the embodiment of figure 1 the second precursor nozzle 10 is arranged to supply second precursor into the deposition chamber 5. In this embodiment the second precursor nozzle is provided as a gas nozzle arranged to supply gaseous second precursor flow into the deposition chamber 5 for providing the coating 2 on the substrate 1. Thus in this embodiment the first precursor is liquid precursor and the first precursor is atomized into droplets 8 for providing the first precursor flow comprising droplets 8 and the second precursor is a gaseous precursor and the second precursor flow is gaseous precursor flow. In figure 1 the second precursor nozzle 10 is arranged inside the deposition chamber 5. The deposition chamber 5 is provided with a throttle 30 for equalizing the first precursor flow in the deposition chamber 5. The throttle 30 is arranged downstream of the first precursor nozzle 7 in the moving direction of the substrate 1. The second precursor nozzle 10 is arranged downstream of the throttle 30 in the moving direction of the substrate 1. In one embodiment the apparatus may further comprise heaters or heating means for providing thermal energy to the deposition chamber such that the liquid precursor droplets may be vaporized before they collide on the surface 34 of the substrate 1. In an alternative embodiment the substrate 1 itself may be have or provided with the thermal energy for vaporizing the liquid droplets before they collide on the surface 34, or the heaters may heat the substrate 1 to a required temperature for vaporizing the droplets.
In the embodiment of figure 1, the second precursor nozzle is arranged to supply water vapor together with the gaseous second precursor. In one embodiment the second precursor nozzle 10 is arranged to supply the second precursor flow and the water vapor flow separately to the deposition chamber 5 such that the water vapor flow and the second precursor flow are mixed together in the deposition chamber 5 before the second precursor reacts on the surface 34 of the substrate 1. Alternatively the apparatus of figure 1 may comprise a mixer for mixing the second precursor flow and the water vapor flow together before the second precursor nozzle 10. Figure 1 shows a first precursor supply line 23 through which a first precursor flow is supplied to the first precursor nozzle 7 from a first precursor source (not shown), a second precursor supply line 21 through which the second precursor flow is supplied from a second precursor source (not shown) to the second precursor nozzle 10 and a water supply line 22 through which flow or water vapor flow is supplied from a water source (not shown) to the second precursor nozzle 10. The second precursor supply line 21 and the water supply line 22 are connected to each other upstream of the second precursor nozzle 10 for mixing the water flow and the second precursor flow before supplying them to the deposition chamber 5. Preferably the water flow and the precursor flow are mixed in the vicinity of the second precursor nozzle 10. The mixer may be arranged to mix the water flow and the second precursor flow together prior the second precursor nozzle 10. Alternatively the second precursor nozzle 10 may be arranged to mix water vapor flow and the second precursor flow together during supplying the second precursor flow from the second precursor nozzle 10. Therefore second precursor nozzle 10 may be provided to supply the second precursor and the water vapor from different sources such that the water vapor and the second precursor are mixed during or after supplying them from the second precursor nozzle 10. This means that the second precursor flow and the water vapor flow are mixed before the second precursor or the precursors react on the surface 34 of the substrate 1. However, it should be noted that the second precursor nozzle may be arranged to mix liquid water flow to the gaseous second precursor flow during the supply, or alternative the second precursor flow may be arranged to atomize liquid water flow to water droplets and supply the water droplets to the deposition chamber 5 together with the second precursor flow or separately from the second precursor flow such that the water droplets flow and the gaseous second precursor flow are mixed together in the deposition chamber 5. The first and second precursor source and the water source are separate sources and they may be or comprise a container, a liquid container, a gas container or the like. Figure 3 shows another embodiment of an apparatus according to the present invention. The apparatus of figure 3 comprises substantially the same components as the apparatus of figure 1. In this embodiment the apparatus comprises a second precursor nozzle 10 and a separate water nozzle 11. In this embodiment the first precursor supply line 23 supplies first precursor separately to the first precursor nozzle 7, the second precursor supply line 21 supplies second precursor separately to the second precursor nozzle 10, and the water supply line 22 supplies water to the water nozzle 11. The second precursor nozzle 10 is provided as gas nozzle for supplying second gaseous precursor into the deposition chamber 5. The water nozzle 11 of figure 3 is arranged to supply water vapor into the deposition chamber 5. Accordingly, the water nozzle 11 and the second precursor nozzle 10 are arranged such that the water flow and the second precursor flow are mixed together in the deposition chamber 5, or reaction space, before the second precursor react on the surface 34 of the substrate 1. The terms water flow and precursor flow mean the material flow from a water source or precursor source until the water or precursor reach the surface of the substrate in the deposition chamber 5 or until the water or precursor takes part in the surface reactions on the surface 34 of the substrate 1.
In figure 3 both the second precursor nozzle 10 and the water nozzle are located inside the deposition chamber 5. Furthermore, the second precursor nozzle 10 is arranged downstream of the first precursor nozzle 7 in the moving direction of the substrate 1. Also the water nozzle 11 is arranged downstream of the first precursor nozzle 7 in the moving direction of the substrate 1. The second precursor nozzle 10 is arranged downstream of the water nozzle 11, but in another embodiment they may be arranged oppositely. The second precursor nozzle 10 and the water nozzle 11 are arranged downstream of the throttle 30 in the moving direction of the substrate 1.
Figure 4 shows another embodiment of the present invention, in which the first precursor is liquid precursor and the first precu rsor is atomized into droplets 8 for providing the first precursor flow comprising droplets 8 and the second precursor is liquid precursor and the second precursor is atomized into droplets 13 for providing the second precursor flow comprising droplets 13. Therefore, the first precursor nozzle 7 comprises an atomizer for atomizing the first liquid precursor into dropl ets 8 and the second precursor nozzle 10 comprises an atomizer for atomizing the second liquid precursor into droplets 13. The first and second precursor nozzle 7, 10 are preferably arranged to produce droplets 8, 13 having the average aerodynamic diameter less than 10 micrometers, preferably 3 micrometres or less, more preferably 1 micrometre or less. The atomizer of figure 2 may be used for producing the droplets 8, 13. The apparatus 3 further comprises a second conduit 9 for transporting the second precursor flow from the second precursor nozzle 10 to the deposition chamber 5 or towards the surface 34 of the substrate 1. As shown in figure 4, the second precursor nozzle 10 is arranged to the second conduit 9. The second precursor conduit 9 may thus form a second atomization chamber which is in fluid communication with the deposition chamber 5 for conducting the first precursor flow to the deposition chamber 5. The second precursor conduit 9 may thus form part of the deposition chamber or reaction space 5.
In figure 4 the apparatus is further arranged to mix water flow to the second precursor flow. The water flow may be mixed to the liquid second precursor flow before, during or after supplying the second precursor from the second precursor nozzle 10 to the deposition chamber 5. Figure 4 shows an embodiment in which the second precursor nozzle 10 may be arranged to supply water flow and second precursor flow from different sources such that second precursor flow and the water flow are mixed during or after atomization in the second precursor nozzle 10. The second precursor is supplied to the second precursor nozzle 10 via the second precursor supply line 21 and the water flow is supplied to the second precursor nozzle 10 via water supply line 22 separately from the second precursor flow. In this case the water may be supplied as water vapour flow or as liquid water flow which is atomized into water droplets. The second precursor nozzle 10 may arranged to supply both second precursor flow and water flow separately to the deposition chamber 5 such that the second precursor flow and the water flow are mixed in the deposition chamber 5. Alternatively the at least one second precursor nozzle 10 is arranged to mix the second precursor flow and water flow together and supply the mixture to the deposition chamber 5. Alternatively the water flow and the second precursor flow may be mixed before or upstream of the second precursor nozzle 10 such that the second precursor nozzle 10 atomizes the mixture of the second precursor flow and water flow into droplets 13 for supplying second precursor flow comprising water and second precursor to the deposition chamber 5, as shown in connection with figure 1. The second precursor nozzle 10 is arranged downstream of the first precursor nozzle 7. The second precursor nozzle 10 may be further arranged downstream of the throttle 30 in the moving direction of the substrate 1.
As shown in figure 4 the apparatus further comprises charging means for electrically charging the droplets 8. The charging means may also be arranged to charge both the first precursor droplets 8 and second precursor 13, or only droplets 13. The charging means are arranged to electrically charge the droplets 8 by a charger 101 and an electric field created between electrode 103 and coelectrode 104 is used to guide droplets 8 towards to the surface 34 of substrate 1. In a preferred embodiment, the charger 101 is a corona charger and the required high voltage is supplied from a high voltage generator 102. Figure 5 shows another embodiment of the apparatus 3 according to the present invention. In figure 5 the first precursor is liquid precursor and the first precursor is atomized into droplets 8 for providing the first precursor flow comprising droplets 8 and the second precursor is liquid precursor and the second precursor is atomized into droplets 8 for providing the second precursor flow comprising droplets 13. The embodiment of figure 5 corresponds the apparatus of figure 4, except that the there is a separate water nozzle 11 arranged to the second conduit. The first precursor supply line 23 supplies first precursor separately to the first precursor nozzle 7, the second precursor supply line 21 supplies second precursor separately to the second precursor nozzle 10, and the water supply line 22 supplies water to the water nozzle 11. In this embodiment liquid water is supplied from the water nozzle 11 for providing a water flow into the deposition chamber 5. The second precursor nozzle 10 and the water nozzle 11 are arranged such that the second precursor flow and the water flow are mixed in the second conduit 9 or further in the deposition chamber 5, or reaction space. The water flow and the second precursor flow may be supplied towards the surface 34 of the substrate such that they mix together before the surface 34 of the substrate, preferably in the second conduit 9. The water nozzle 11 may comprise an atomizer for atomizing liquid form water into water droplets for providing a water flow comprising water droplets . In an alternative embodiment the water nozzle 11 may also be arranged to supply water vapor, thus it may be a gas nozzle.
Figure 6 shows yet another embodiment of the present invention, in which the first precursor is liquid precursor and the first precu rsor is atomized into droplets 8 for providing the first precursor flow comprising droplets 8 and the second precursor is liquid precursor and the second precursor is atomized into droplets 13 for providing the second precursor flow comprising droplets 13. Therefore, the first precursor nozzle 7 comprises an atomizer for atomizing the first liquid precursor into dropl ets 8 and the second precursor nozzle 10 comprises an atomizer for atomizing the second liquid precursor into droplets 13. In this embodiment the apparatus 3 is further provided with a separate water nozzle 11 arranged to supply water vapor into the deposition chamber 5. The first precursor supply line 23 supplies first precursor separately to the first precursor nozzle 7, the second precursor supply line 21 supplies second precursor separately to the second precursor nozzle 10, and the water supply line 22 supplies water separately to the water nozzle 11. The water nozzle 11 and the second precursor nozzle 10 are arranged such that the water vapor flow and the second precursor flow are mixed in the deposition chamber 5. In figure 6 the water nozzle 11 is arranged downstream of the first precursor nozzle 7 in the moving direction of the substrate 1. The second precursor nozzle 10 is further arranged downstream of the water nozzle 11. The second precursor nozzle 10 and the water nozzle 11 are arranged downstream of the throttle 30 in the moving direction of the substrate 1. Thus there is a throttle arranged between the first precursor nozzle 7 and the second precursor nozzle, or between the first precursor nozzle 7 and the water nozzle 11.
Figure 7 shows another embodiment of the present invention, in which the first precursor is liquid precursor and the first precursor is atomized into droplets 8 for providing the first precursor flow comprising droplets 8 and the second precursor is liquid precursor and the second precursor is atomized into droplets 13 for providing the second precursor flow comprising droplets 13. The first and second precursor nozzle 7, 10 are arranged to atomize and supply the first and precursors to the same the first conduit 6, which may be an atomization chamber. Therefore, the first precursor nozzle 7 comprises an atomizer for atomizing the first liquid precursor into droplets 8 and the second precursor nozzle 10 comprises an atomizer for atomizing the second liquid precursor into droplets 13. In this embodiment the apparatus 3 is further provided with a separate water nozzle 11 arranged to supply water vapor into the deposition chamber 5. The first precursor supply line 23 supplies first precursor separately to the first precursor nozzle 7, the second precursor supply line 21 supplies second precursor separately to the second precursor nozzle 10, and the water supply line 22 supplies water separately to the water nozzle 11. The first precursor nozzle 7 and the second precursor nozzle 10 are arranged such that the first and second precursor flows are mixed in the deposition chamber 5. In figure 6 the water nozzle 11 is arranged downstream of the first and second precursor nozzle 7, 10 in the moving direction of the substrate 1 such that the water or water vapor is mixed to the mixture of the first and second precursor flows. The water nozzle 11 is arranged downstream of the throttle 30 in the moving direction of the substrate 1. Figure 8 shows an alternative embodiment in which the second precursor nozzle 10 and the water nozzle have changed places in relation to the embodiment of figure 7. Figure 9 further shows an embodiment in which water supply line 22 is connected to the second precursor supply line 21 for supplying water and second precursor into the deposition chamber 5 via the second precursor nozzle 10. Accordingly the apparatus of the present invention comprise a deposition chamber first precursor supply means 7, 23 for providing a first precursor flow, the first precursor flow comprising at least one first precursor material for providing the coating and second precursor supply means 10, 21 for providing a second precursor flow, the second precursor flow comprising at least one second precursor material for providing the coating, the second precursor nozzle being arranged to supply the second precursor flow sepa rately from the first precursor flow. It should be noted that the apparatus may also comprise a mixing chamber (not shown) for mixing the first and second precursor flow before the precursors react on the surface 34 of the substrate 1. The mixing chamber forms part of the deposition chamber 5. The mixing chamber may also alternatively be arranged for mixing the second precursor flow and the water flow together before the precursors react on the surface 34 of the substrate 1, or the first and second precursor flow and the water flow. Furthermore, in some embodiments the first precursor may be a gaseous precursor, and that the first precursor nozzle 7 comprises a gas nozzle for providing the first gaseous precursor flow. One example for using the process and apparatus according to the present invention is in manufacturing transparent conductive oxide (TCO) coatings on glass substrates. When manufacturing chemical vapor deposited coatings, such as TCO coatings, the precursor droplets are preferably evaporated before they collide on the surface of the substrate. However, when manufacturing coatings which are based on the decomposition of a precursor, such as cadmium sulfide (CdS) coatings, it is preferred to allow the droplets to hit the surface. The present invention is valid in both coating processes. An example of TCO coatings is fluorine doped tin oxide (FTO) coating provided from an organic compound of tin, such as monobutyltin trichloride (MBTC) and a tin-doping fluorine source, such as hydrogen fluorine (HF) or an organic source, such as trifluoroacetic acid (TFA, C2H F3O2) . MBTC and TFA cannot be mixed together without an additional solvent, which usually comprises oxygen, such as methyl alcohol (CH3OH) . However, the process and apparatus described in the present invention allows using MBTC as the first precursor and TFA as the second precursor. Thus MBTC and TFA are supplied separately to the deposition chamber 5 and furthermore TFA is supplied together with a water to the deposition chamber 5. Water radically increases the coating growth rate of FTO coatings. When the FTO coating is formed on glass substrates at relatively low temperatures (below 650°C), it is preferred to supply water in vapor form, because evaporating the water droplets is energy-consuming and would thus cool down the surface of the glass substrate, which is unfavorable to the coating growth. The mixture of MBTC and TFA is highly corrosive and the in the present invention they are mixed at the deposition chamber, not in the supply means. In the present invention a first precursor flow is supplied towards the surface 34 of the substrate 1 and a second precursor flow is supplied towards the surface 34 of the substrate 1 separately from the first precursor flow. Water flow is added or mixed to the second precursor flow in the deposition chamber 5 or before or during the supply from the second precursor nozzle 10 before the second precursor reacts on the surface 34 of the substrate 1. Furthermore, the apparatus and process may be arranged to first subjecting the surface 34 of the substrate 1 to the first precursor flow and then to the second precursor flow or the second precursor flow and the water flow, or mixing the first and second precursor flow before the precursors react on the surface 34 of the substrate 1, or mixing the first precursor flow, second precursor flow and the water flow together before the precursors react on the surface 34 of the substrate 1 . It should be noted that water may be supplied to the deposition chamber as liquid form or as vapor. Furthermore the first and/or second are supplied to the to the deposition chamber as liquid form or as vapor, such that at least one of them is supplied as liquid droplets or solid particles. It is apparent to a person skilled in the art that as technology advanced, the basic idea of the invention can be implemented in various ways. The invention and its embodiments are therefore not restricted to the above examples, but they may vary within the scope of the claims.

Claims

Claims
1. An aerosol-assisted process for providing a coating (2) on a substrate (1) in which process precursors react on a surface (34) of the substrate (1) for providing the coating (2), the process comprising : - providing a first precursor flow and supplying the first precursor into a reaction space (5) for subjecting the substrate (1) to the first precursor flow in the reaction space (5), the first precursor flow comprising at least one first precursor material for providing the coating (2) ; and
- providing a second precursor flow and supplying the second precursor flow into the reaction space (5) for subjecting the substrate ( 1) to the second precursor flow in the reaction space (5), the second precursor flow being separate from the first precursor flow, the second precursor flow comprising at least one second precursor material , characterized by: - providing a water flow, the water flow being separate from the first precursor flow and the second precursor flow; and
- supplying the water flow into the reaction space (5) for accelerating the surface reactions providing the coating (2).
2. A process according to claim 1, characterized in that : - the water flow is supplied into the reaction space (5) separately from the first and second precursor flows and mixed to the first or second precursor flow in the reaction space (5) ; or
- the water flow is mixed to the first or second precursor flow at an inlet (10, 11) of the reaction space (5) during supplying the second precursor flow into the reaction space (5) ; or - the water flow is mixed to the first or second precursor flow upstream of the reaction space (5) or in the reaction space (5) .
3. A process according to claim 1 or 2, characterized by mixing the water flow and the first or second precursor flow in the reaction space ( 5) before the first or second precursor reacts on the surface (34) of the substrate (1).
4. A process according to any one of claims 1 to 3, characterized in that
- the first precursor is different from the second precursor; or
- the second precursor comprises at least one first precursor material different from the precursor materials of the second precursor.
5. A process according to any one of claims 1 to 4, characterized by
- supplying the first precursor flow towards the surface (34) of the substrate (1) ; and
- supplying the second precursor flow towards the surface (34) of the substrate (1) separately from the first precursor flow .
6. A process according to any one of claims 1 to 5, characterized in that:
- the first precursor is liquid precursor and the first precursor is atomized into droplets (8) for providing the first precursor flow comprising droplets (8) and the second precursor is liquid precursor and the second precursor is atomized into droplets (8) for providing the second precursor flow comprising droplets (13) ; or
- the first precursor is liquid precursor and the first precursor is atomized into droplets (8) for providing the first precursor flow comprising droplets (8) and the second precursor is a gaseous precursor and the second precursor flow is gaseous precursor flow; or - the first precursor is a gaseous precursor and the first precursor flow is gaseous precursor flow and the second precursor is liquid precursor and the second precursor is atomized into droplets (8) for providin g the second precursor flow comprising droplets (13) .
7. A process according to any one of claims 1 to 6, characterized by
- providing the water flow as a water vapor flow; or
- providing the water flow as liquid water flow and atomizing the water flow to droplets into the reaction space (5) .
8. A process according to claim 7, characterized in that - the water flow is a water vapor flow and the water vapor flow is mixed to the liquid first or second precursor flow or in the reaction space (5) to liquid first or second precursor flow atomized into the reaction space (5); or
- the water flow is a water vapor flow and the water vapor flow is mixed to the gaseous first or second precursor flow; or
- the water flow is a liquid water flow and the liquid water vapor flow is mixed to the liquid first or second precursor flow or liquid water is atomized into the reaction space (5) and mixed in the reaction space to liquid first or second precursor flow atomized into the reaction space (5); or
- the water flow is a liquid water flow and the liquid water vapor flow is mixed to the gaseous first or second precursor flow.
9. A process according to any one of claims 1 to 8, characterized by:
- first subjecting the surface (34) of the substrate (1) to the first precursor flow and then to the mixture of the second precursor flow and the water flow; or - first subjecting the surface (34) of the substrate (1) to the mixture of the first precursor flow and the water flow and then to the second precursor flow; or
- mixing the first and second precursor flow before the precursors react on the surface (34) of the substrate (1) ; or
- mixing the first precursor flow, second precursor flow and the water flow together before the precursors react on the surface (34) of the substrate (1) .
10. A process according to any one of claims 1 to 9, characterized in that the first precursor comprises monobutyltin trichloride (MBTC) and the second precursor comprises fluorine.
11. A process according to claim 10, characterized in that the second precursor comprises hydrogen fluorine (HF) or trifluoroacetic acid (TFA).
12. A process according to any one of claims 1 to 11, characterized by forming solid particles from the first liquid precursor or the second liquid precursor or the first and second liquid precursors by first atomizing the liquid precursor in to droplets and conducting the formed droplets to a thermal reactor such that at least part of the first or second precursor is supplied to the surface (34) of the substrate (1) as solid particles.
13. An apparatus (3) for coating a substrate (1) with an aerosol -assisted deposition process in which process precursor materials react on a surface (34) of the substrate (1) for providing a coating (2) on the substrate (1), the apparatus (3) comprising :
- a deposition chamber (5); - first precursor supply means (7, 23) for providing a first precursor flow, the first precursor flow comprising at least one first precursor material for providing the coating (2) ; and - second precursor supply means (10, 21) for providing a second precursor flow, the second precursor flow comprising at least one second precursor material for providing the coating (2), the second precursor nozzle (10) being arranged to supply the second precursor flow separately from the first precursor flow, characterized in that the apparatus (3) further comprises water supply means (11, 22) for providing a water flow, which is separate from the first and second precursor flow, and that the water supply means (11, 22) are arranged to supply the water flow into the deposition chamber (5) for accelerating the surface reactions providing the coating (2).
14. An apparatus according to claim 13, characterized in that the water supply means (11, 22) comprise at least one water nozzle (11) for supplying the water flow into the deposition chamber (5), the first precursor supply means (7, 23) comprise at least one first precursor nozzle (7) for supplying the first precursor flow into the deposition chamber (5) and the second precursor supply means (10, 21) comprise at least one second precursor nozzle ( 10) for supplying the second precursor flow into the deposition chamber (5), and that the at least one water nozzle (11) and the first or second precursor nozzle (7, 10) are arranged such that the first or second precursor flow and the water flow are mixed in the deposition chamber (5) .
15. An apparatus according to claim 13, characterized in
- that the first precursor supply means (7, 23) comprise at least one first precursor nozzle (7) for supplying the first precursor flow into the deposition chamber (5) and the second precursor supply means (10, 21) comprise at least one second precursor nozzle ( 10) for supplying the first precursor flow into the deposition chamber (5); and
- that the at least one first or second precursor nozzle (7, 10) is arranged to supply both first or second precursor flow and water flow separately to the deposition chamber (5) such that the second precursor flow and the water flow are mixed into the deposition chamber (5), or that the at least one first or second precursor nozzle (7, 10) is arranged to mix the first or second precursor flow and water flow together and supply the mixture into the deposition chamber (5).
16. An apparatus according to claim 13, characterized in that the water supply means (11, 22) and the first precursor supply means (7, 23) or the second precursor supply means (10, 21) are arranged to mix the water and the first precursor flow or the second precursor upstream of the deposition chamber (5) .
17. An apparatus according to claim 16, characterized in that the apparatus comprises a mixer for mixing the first or second precursor flow and water flow upstream of the first or second precursor nozzle (7, 10) .
18. An apparatus according to any of claims 13 to 17, characterized in that the first precursor is a liquid precursor, and that the first precursor supply means (7, 23) comprise a first precursor nozzle (7) having an atomizer for atomizing the first liquid precursor into droplets (8) ; or that the first precursor is a gaseous precursor, and that the first precursor supply means (7, 23) comprise a first gas nozzle (7) for supplying the first precursor flow into the deposition chamber (5) .
19. An apparatus according to any of claims 13 to 18, characterized in that the second precursor is a liquid precursor, and that the second precursor supply means (10, 21 ) comprise a second precursor nozzle (10) having an atomizer for atomizing the second liquid precursor into droplets (13) ; or that the second precursor is a gaseous precursor, and that the second precursor supply means (10, 21) comprise a second gas nozzle (10) for supplying the first precursor flow into the deposition chamber (5) .
20. An apparatus according to any of claims 13 to 19, characterized in that the water supply means (11, 22) comprise a water nozzle (11), and that the water nozzle ( 11) is a gas nozzle for supplying water vapor into the deposition chamber (5) or the water nozzle (11) comprises an atomizer for atomizing liquid water to water droplets into the deposition chamber (5) .
21. An apparatus according to claim 18 or 19, characterized in that the apparatus further comprises means for forming at least one thermal reactor producing solid particles from the droplets (8, 13) of the first precursor or the second precursor or the first and second precursor such that at least part of the first or second precursor is supplied to the surface (34) of the substrate (1) as solid particles.
22. An apparatus according to any of claims 14 to 21, characterized in that the apparatus comprises a deposition chamber (5) and conveyor means for moving the substrate (1) through the deposition chamber (5), and that the second precursor nozzle ( 10) is arranged downstream of the first precursor nozzle (7) in the moving direction of the substrate (1).
23. An apparatus according to claim 22, characterized in that the water nozzle (11) is arranged downstream of the first precursor nozzle (7) in the moving direction of the substrate (1).
24. An apparatus according to claim 22 or 23, characterized in that the deposition chamber (5) comprises a throttle (30) downstream of the first precursor nozzle (7) in the moving direction of the substrate (1), and that the second precursor nozzle (10) is arranged downstream of the throttle (30) or that the second precursor nozzle ( 10) and the water nozzle ( 11) are arranged downstream of the throttle (30) in the moving direction of the substrate (1).
25. An apparatus according to any of claims 12 to 24, characterized in that the deposition chamber (5) comprises a mixing chamber for mixing the first and second precursor flow or for mixing the first precursor flow, second precursor flow and the water flow together.
PCT/FI2012/050412 2011-04-28 2012-04-26 Process and apparatus for coating WO2012146828A2 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2026454A (en) * 1978-07-20 1980-02-06 Bfg Glassgroup Coating glass with tin oxide
GB2033374A (en) * 1978-10-19 1980-05-21 Bfg Glassgroup Tin oxide coating of glass
US5393563A (en) * 1991-10-29 1995-02-28 Ellis, Jr.; Frank B. Formation of tin oxide films on glass substrates
WO2009080892A1 (en) * 2007-12-20 2009-07-02 Beneq Oy Device for forming aerosol, and method and apparatus for coating glass
WO2009080893A1 (en) * 2007-12-20 2009-07-02 Beneq Oy Device and method for producing aerosol
WO2011027035A1 (en) * 2009-09-03 2011-03-10 Beneq Oy Process and apparatus for controlling coating deposition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2026454A (en) * 1978-07-20 1980-02-06 Bfg Glassgroup Coating glass with tin oxide
GB2033374A (en) * 1978-10-19 1980-05-21 Bfg Glassgroup Tin oxide coating of glass
US5393563A (en) * 1991-10-29 1995-02-28 Ellis, Jr.; Frank B. Formation of tin oxide films on glass substrates
WO2009080892A1 (en) * 2007-12-20 2009-07-02 Beneq Oy Device for forming aerosol, and method and apparatus for coating glass
WO2009080893A1 (en) * 2007-12-20 2009-07-02 Beneq Oy Device and method for producing aerosol
WO2011027035A1 (en) * 2009-09-03 2011-03-10 Beneq Oy Process and apparatus for controlling coating deposition

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