EP4584221A1 - Procédé de dépôt d'une couche - Google Patents

Procédé de dépôt d'une couche

Info

Publication number
EP4584221A1
EP4584221A1 EP23771919.0A EP23771919A EP4584221A1 EP 4584221 A1 EP4584221 A1 EP 4584221A1 EP 23771919 A EP23771919 A EP 23771919A EP 4584221 A1 EP4584221 A1 EP 4584221A1
Authority
EP
European Patent Office
Prior art keywords
mol
process according
glass substrate
gaseous mixture
tin oxide
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP23771919.0A
Other languages
German (de)
English (en)
Inventor
Kelly LAMBRIGHT
David Rimmer
Gary Robert Nichol
Shannon JURCA
Jun Ni
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pilkington Group Ltd
Original Assignee
Pilkington Group Ltd
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 Pilkington Group Ltd filed Critical Pilkington Group Ltd
Publication of EP4584221A1 publication Critical patent/EP4584221A1/fr
Pending legal-status Critical Current

Links

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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • 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
    • C03C17/2453—Coating containing SnO2
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • 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
    • C23C16/4481—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 evaporation using carrier gas in contact with the source material
    • C23C16/4482—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 evaporation using carrier gas in contact with the source material by bubbling of carrier gas through liquid source material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45595—Atmospheric CVD gas inlets with no enclosed reaction chamber
    • 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
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • C03C2218/1525—Deposition methods from the vapour phase by cvd by atmospheric CVD

Definitions

  • This invention relates to a process for depositing a layer on a surface of a substrate.
  • Coatings on substrate surfaces find uses in many fields. Some of the more useful coatings are metal oxides, for example, tin oxide. Some metal oxides (including doped tin oxide) can form transparent conductive oxide (TCO) coatings.
  • TCO transparent conductive oxide
  • Methods used to deposit metal oxide coatings include physical vapour deposition methods, such as sputtering, or liquid based methods, such as sol-gel using spincoating or dip-coating techniques, among others.
  • One particularly useful method for deposition of coatings is chemical vapour deposition (CVD) wherein a fluid precursor in the form of a vapour is delivered to the surface of the substrate where the precursors react and/or decompose thereby depositing a coating.
  • CVD chemical vapour deposition
  • a fluid precursor in the form of a vapour is delivered to the surface of the substrate where the precursors react and/or decompose thereby depositing a coating.
  • CVD chemical vapour deposition
  • Different subsets of CVD include metal organic (MO) CVD, combustion (C) CVD, plasma enhanced (PE) CVD and aerosol-assisted (AA) CVD.
  • DMT Dimethyl tin dichloride
  • DMT is generally supplied as a solid material which requires specialised containers, making transport and storage difficult. It would be beneficial to afford greater versatility in how DMT can be used as a precursor for tin oxide coatings, and consequently how it may be transported and stored.
  • a process for manufacturing a coated glass article comprising: providing a glass substrate having a surface, providing an aqueous solution of dimethyl tin dichloride (DMT), vaporising the aqueous solution of dimethyl tin dichloride to form a gaseous mixture comprising dimethyl tin dichloride and water, delivering the gaseous mixture to the surface of the glass substrate, and depositing a layer based on tin oxide on the surface of the glass substrate, wherein the surface of the glass substrate is at a temperature of at least 550 °C when the gaseous mixture is delivered to said surface of the glass substrate.
  • DMT dimethyl tin dichloride
  • a layer is said to be “based on” a particular material or materials, this means that the layer predominantly consists of the corresponding said material or materials, which means typically that it comprises at least about 50 at.% of said material or materials.
  • compositions consisting essentially of a set of components will comprise less than 5% by weight, typically less than 3% by weight, more typically less than 1% by weight of non-specified components.
  • references herein such as “in the range x to y” are meant to include the interpretation “from x to y” and so include the values x and y.
  • a transparent material or a transparent substrate is a material or a substrate that is capable of transmitting visible light so that objects or images situated beyond or behind said material can be distinctly seen through said material or substrate.
  • the “thickness” of a layer is, for any given location at a surface of the layer, represented by the distance through the layer, in the direction of the smallest dimension of the layer, from said location at a surface of the layer to a location at an opposing surface of said layer.
  • a “derivative” is a chemical substance related structurally to another chemical substance and theoretically derivable from it.
  • the surface of the glass substrate is at a temperature of at least 570 °C, more preferably at least 580 °C, even more preferably at least 590 °C, most preferably at least 600 °C, but preferably at most 800 °C, more preferably at most 750 °C, even more preferably at most 730 °C, most preferably at most 720 °C.
  • the surface of the glass substrate is at a temperature of at least 580 °C but at most 750 °C. Depositing a layer when the substrate is at these preferred temperatures affords greater crystallinity of the layer, which can improve toughenability (resistance to heat treatment).
  • the sheet resistance exhibited by the coated glass article is measured on the surface of the glass substrate upon which the layer based on tin oxide has been deposited.
  • the sheet resistance exhibited by the coated glass article can be measured using a 4-point probe method and a commercially available 4-point probe.
  • the Fe2C>3 level by weight is typically 0.11%.
  • Float glass with an Fe2C>3 content less than about 0.05% by weight is typically referred to as low iron float glass.
  • Such glass usually has the same basic composition of the other component oxides i.e. low iron float glass is also a soda-lime-silicate glass, as is clear float glass.
  • low iron float glass has less than 0.02% by weight Fe2C>3.
  • the glass pane is a borosilicatebased glass pane, an alkali-aluminosilicate-based glass pane, or an aluminium oxidebased crystal glass pane.
  • the process is carried out using Chemical Vapour Deposition (CVD).
  • the CVD may be carried out in conjunction with the manufacture of the substrate, preferably a transparent glass substrate.
  • the glass substrate may be formed utilizing the well-known float glass manufacturing process.
  • the process is carried out during the float glass manufacturing process.
  • the glass substrate may also be referred to as a glass ribbon.
  • the CVD may be carried out either in the float bath, in the lehr or in the lehr gap.
  • the preferred method of CVD is atmospheric pressure CVD (e.g. online CVD as performed during the float glass process).
  • the CVD process can be utilised apart from the float glass manufacturing process or well after formation and cutting of the glass ribbon.
  • the CVD may be carried out during the float glass production process at substantially atmospheric pressure.
  • the CVD may be carried out using low-pressure CVD or ultrahigh vacuum CVD.
  • the CVD may be carried out using aerosol assisted CVD or direct liquid injection CVD.
  • the CVD may be carried out using microwave plasma-assisted CVD, plasma-enhanced CVD, remote plasma-enhanced CVD, atomic layer CVD, combustion CVD (flame pyrolysis), hotwire CVD, metalorganic CVD, rapid thermal CVD, vapour phase epitaxy, or photo-initiated CVD.
  • the glass substrate will usually be cut into sheets after deposition of any CVD layer(s) for storage or convenient transport.
  • the bath section may include a bottom section within which a bath of molten tin is contained, a roof, opposite sidewalls, and end walls. It is understood that the bath may include other suitable materials to achieve the desired results.
  • the roof, side walls, and end walls together may define an enclosure in which a non-oxidizing atmosphere is maintained to prevent oxidation of the molten tin.
  • a coating apparatus comprising gas distributor beams may be located in the bath section. Gas distributor beams in the bath section may be employed to apply the layer based on tin oxide by the process of the presently described subject matter or additional coatings onto the substrate prior to, or after, applying the layer based on tin oxide.
  • a suitable non-oxidizing atmosphere generally nitrogen or a mixture of nitrogen and hydrogen in which nitrogen predominates, may be maintained to prevent oxidation of the molten tin.
  • the atmosphere gas may be admitted through conduits operably coupled to a distribution manifold.
  • the non-oxidizing atmosphere gas may be introduced at a rate sufficient to compensate for normal losses and maintain a slight positive pressure, on the order of about 0.001 to about 0.01 atmospheres above ambient atmospheric pressure, so as to prevent infiltration of outside atmosphere.
  • the above-noted pressure range is considered to constitute normal atmospheric pressure.
  • Heat for maintaining the desired temperature regime in the tin bath and the enclosure may be provided by radiant heaters within the enclosure and the glass ribbon itself.
  • a configuration for the distributor beams suitable for supplying precursor materials in accordance with the presently described subject matter is an inverted, generally channel-shaped framework formed by spaced inner and outer walls and defining two enclosed cavities.
  • a suitable heat exchange medium may be circulated through the enclosed cavities in order to maintain the distributor beams at a desired temperature.
  • the gaseous mixture is delivered to the coating apparatus.
  • the gaseous mixture is fed through a coating apparatus and discharged from the coating apparatus utilizing one or more gas distributor beams prior to deposition of the layer based on tin oxide.
  • the gaseous mixture is formed prior to being fed through the coating apparatus.
  • the aqueous solution of dimethyl tin dichloride may be vaporised and delivered to a feed line connected to an inlet of the coating apparatus.
  • Molecular oxygen and/or a carrier gas such as nitrogen may be delivered to the feed line and mixed with the DMT and water.
  • the gaseous mixture may be formed within the coating apparatus.
  • the gaseous mixture may be supplied through a supply conduit.
  • the supply conduit may be surrounded by a cooling fluid.
  • the supply conduit may extend along the distributor beam and admit the gaseous mixture through drop lines spaced along the supply conduit.
  • the supply conduit may lead to a delivery chamber within a header carried by the framework.
  • the gaseous mixture admitted through the drop lines may be discharged from the delivery chamber through a passageway toward a coating chamber defining a vapor space opening onto the glass substrate where the gaseous mixture flows along the surface of the substrate.
  • Baffle plates may be provided within the delivery chamber for equalizing the flow of the gaseous mixture across the distributor beam to assure that the gaseous mixture is discharged against the glass substrate in a smooth, laminar, uniform flow entirely across the distributor beam.
  • Spent precursor gases may be collected and removed through exhaust chambers along the sides of the distributor beam.
  • the gaseous mixture is introduced through a gas supply duct where it is cooled by cooling fluid circulated through a plurality of ducts.
  • the gas supply duct may open through an elongated aperture into a glass flow restrictor.
  • the gas flow restrictor may comprise a plurality of metal strips longitudinally crimped in the form of a sine wave and vertically mounted in abutting relationship with one another extending along the length of the distributor. Adjacent crimped metal strips may be arranged “out of phase” to define a plurality of vertical channels between them. These vertical channels may be of small cross-sectional area relative to the cross-sectional area of the gas supply duct, so that the gaseous mixture is released from the gas flow restrictor at substantially constant pressure along the length of the distributor.
  • the gaseous mixture may be released from the gas flow restrictor into the inlet side of a substantially U-shaped guide channel generally comprising an inlet leg of a coating chamber which opens onto the glass substrate, and at least one exhaust leg, whereby used precursor gases are withdrawn from the glass.
  • the guide channel may have any suitable size, shape, and configuration as desired. The rounded corners of the blocks defining the coating channel promote a uniform laminar flow of coating parallel to the glass substrate surface.
  • the layer based on tin oxide is deposited on the surface of the glass substrate at a deposition rate of at least 2 nm per second, more preferably at least 5 nm per second, even more preferably at least 7 nm per second.
  • the layer based on tin oxide comprises, more preferably consists essentially of, even more preferably consists of, tin (IV) oxide.
  • the layer based on tin oxide may comprise doped tin oxide and/or may comprise a mixed oxide.
  • the doped tin oxide may be doped with one or more of fluorine, indium, antimony, boron, manganese, zinc, aluminium, chromium, phosphorus, strontium or cadmium.
  • the doped tin oxide is doped with one or more of fluorine, indium or antimony. More preferably the doped tin oxide is doped with fluorine.
  • the gaseous mixture also comprises HF and/or trifluoro acetic acid. Doping the layer based on tin oxide can enable said layer to become electrically conductive.
  • the layer based on tin oxide comprises at least 0.2 atomic% dopant, more preferably at least 0.4 atomic% dopant, even more preferably at least 0.6 atomic% dopant, most preferably at least 0.8 atomic% dopant, but preferably at most 5 atomic% dopant, more preferably at most 2 atomic% dopant, even more preferably at most 1.5 atomic% dopant, most preferably at most 1.2 atomic% dopant.
  • These preferred ranges can provide advantages for solar cell applications in terms of optimising cell efficiency.
  • the layer based on tin oxide may be deposited directly on the surface of the glass substrate.
  • said layer based on tin oxide may be deposited indirectly on the surface of the glass substrate i.e. said layer based on tin oxide may be deposited over one or more previously deposited layers.
  • said layer based on tin oxide may be deposited over, and preferably directly contacts, a layer based on silica.
  • said layer based on tin oxide is deposited over, and directly contacts, a layer based on silica, wherein said layer based on silica has been deposited over, and directly contacts, a further layer based on tin oxide.
  • said surface of the glass substrate is the gas side surface.
  • Coated glass manufacturers usually prefer depositing coatings on the gas side surface (as opposed to the tin side surface for float glass) because deposition on the gas side surface can improve the properties of the coating.
  • the coated glass article may exhibit a low haze value.
  • the term “haze” refers to the percentage of incident visible light that scatters when passing through the coated glass article.
  • the haze exhibited by the coated glass article is measured from the surface of the glass substrate upon which the layer based on tin oxide has been deposited.
  • the coated glass article may exhibit haze of 0.5% or less.
  • the coated glass article exhibits a haze of 0.4% or less.
  • the haze exhibited by the coated glass article is 0.1 -0.4%.
  • the haze exhibited by the coated glass article can be measured using a commercially available haze meter such as the BYK-Gardner haze-gard plus. Any invention described herein may be combined with any feature of any other invention described herein mutatis mutandis.
  • FIG. 3 is a schematic view, in vertical section, of an installation for practicing the float glass process which incorporates several OVD apparatuses for manufacturing a coated glass article in accordance with certain embodiments of the present invention.
  • Figure 1 shows a cross-section of a coated glass article 1 according to certain embodiments of the present invention.
  • Coated glass article 1 comprises a transparent float glass substrate 2 that has been coated using CVD with a layer based on tin oxide 3.
  • Coated glass article 1 comprises a transparent float glass substrate 2 that has been sequentially coated using CVD with a layer based on silica 4 and a layer based on tin oxide 3.
  • the process of the present invention may be carried out using CVD in conjunction with the manufacture of the glass substrate in the float glass process.
  • the float glass process is typically carried out utilizing a float glass installation such as the installation 10 depicted in Figure 3.
  • a float glass installation such as the installation 10 depicted in Figure 3.
  • the float glass installation 10 described herein is only illustrative of such installations.
  • the float glass installation 10 may comprise a canal section
  • the glass ribbon 8 advances from the bath section 11 through an adjacent annealing lehr 12 and a cooling section 13.
  • the float bath section 11 includes: a bottom section 14 within which a bath of molten tin 15 is contained, a roof 16, opposite side walls (not depicted) and end walls 17.
  • the roof 16, side walls and end walls 17 together define an enclosure 18 in which a nonoxidizing atmosphere is maintained to prevent oxidation of the molten tin 15.
  • the molten glass 19 flows along the canal 20 beneath a regulating tweel
  • the molten glass 19 spreads laterally under the influence of gravity and surface tension, as well as certain mechanical influences, and it is advanced across the tin bath 15 to form the glass ribbon 8.
  • the glass ribbon 8 is removed from the bath section 11 over lift out rolls 22 and is thereafter conveyed through the annealing lehr 12 and the cooling section 13 on aligned rolls.
  • the deposition of coatings preferably takes place in the float bath section 11 , although it may be possible for deposition to take place further along the glass production line, for example, in the gap 28 between the float bath 11 and the annealing lehr 12, or in the annealing lehr 12.
  • CVD apparatuses 9, 9A, 9B, 9C are shown within the float bath section 11 .
  • CVD apparatuses 9, 9A, 9B, 9C are shown within the float bath section 11 .
  • One or more additional coating apparatuses may be provided.
  • One or more CVD apparatus may alternatively or additionally be located in the lehr gap 28. Any by-products are removed through coater extraction slots and then through a pollution control plant.
  • a silica layer is formed utilizing using CVD apparatus 9A and a fluorine doped tin oxide layer is formed utilizing CVD apparatus 9.
  • a suitable non-oxidizing atmosphere generally nitrogen or a mixture of nitrogen and hydrogen in which nitrogen predominates, may be maintained in the float bath section 11 to prevent oxidation of the molten tin 15 comprising the float bath.
  • the atmosphere gas is admitted through conduits 23 operably coupled to a distribution manifold 24.
  • the non-oxidizing gas is introduced at a rate sufficient to compensate for normal losses and maintain a slight positive pressure, on the order of between about 0.001 and about 0.01 atmosphere above ambient atmospheric pressure, so as to prevent infiltration of outside atmosphere.
  • the above-noted pressure range is considered to constitute normal atmospheric pressure.
  • CVD is generally performed at essentially atmospheric pressure.
  • the pressure of the float bath section 11, annealing lehr 12, and/or in the gap 28 between the float bath is generally performed at essentially atmospheric pressure.
  • the annealing lehr 12 may be essentially atmospheric pressure. Heat for maintaining the desired temperature regime in the float bath section 11 and the enclosure 18 is provided by radiant heaters 25 within the enclosure 18.
  • the atmosphere within the lehr 12 is typically atmospheric air, as the cooling section 13 is not enclosed and the glass ribbon 8 is therefore open to the ambient atmosphere.
  • the glass ribbon 8 is subsequently allowed to cool to ambient temperature. To cool the glass ribbon 8, ambient air may be directed against the glass ribbon 8 by fans 26 in the cooling section 13. Heaters (not shown) may also be provided within the annealing lehr
  • aqueous DMT 50 %.wt/wt, Galata
  • nitrogen compressed liquid, Air Products
  • oxygen PT# Ox ED300, extra dry, AirGas
  • Aqueous DMT was used directly as the precursor for atmospheric pressure chemical vapor deposition of SnO2 thin films on SiO2 coated low-iron soda-lime float glass plates (2.8 mm x 20.3 cm x 61.0 cm, “the substrate”) using an on-line mini dynamic coater.
  • the substrate was mounted onto an electronically controlled ceramic conveyer “boat” that moved through the components of the coating furnace. First the substrate paused in the pre-heat section until it reached 620 °C and then moved into the main furnace which is maintained at the same temperature.
  • the substrate either moved at a line speed of 190.5 cm/min (preferably 63.5 to 889 cm/min, more preferably 190.5 to 508 cm/min) or was stationary for 15 or 20 seconds while the gaseous mixture exited a 15.2 cm precursor nozzle, thus depositing a dynamic or static coating, respectively.
  • a dynamic coating was prepared. From the main furnace the coated glass article moved into the annealing section, where it remained until it decreased to a set temperature (400 °C) and then exited the furnace to be fan cooled.
  • the gaseous mixture was prepared as follows: Nitrogen carrier gas was piped through to a stainless steel (316 steel) pressure pot that was used as for aqueous dimethyltin dichloride containment and delivery. Using a sapphire rotameter, aqueous dimethyltin dichloride was metered into a tube evaporator set to 350 °F (176.7 °C). Additional nitrogen gas was flowed through the barrel of the evaporator to carry the dimethyltin dichloride and water vapors to the coater head via heated lines (200-220 °C) and a 4- way connector in a 200 °C oven. Oxygen gas was combined with the DMT, water and nitrogen vapors just before the 4-way connector. After each deposition water from a metered pressure pot was used to purge the system.
  • Examples were prepared using five different sets of conditions, as shown below in Table 1 , such that the proportions of DMT and water in the gaseous mixture were varied. Each example was prepared on three different occasions and average measurements of thickness and efficiency were determined. Table 1 shows the proportions of each component in the gaseous mixture, with nitrogen making up the balance. Table 1 also shows the flow rates for each component, average thickness of the deposited tin oxide layers and average deposition efficiency. The deposition efficiency is essentially the percentage of the moles of DMT in the gaseous mixture that actually deposit onto the substrate as tin oxide per minute. The area coated is defined by the width of the glass and its line speed.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un article en verre revêtu, ledit procédé consistant à : fournir un substrat de verre ayant une surface, fournir une solution aqueuse de dichlorure de diméthylétain (DMT), vaporiser la solution aqueuse de dichlorure de diméthylétain pour former un mélange gazeux comprenant du dichlorure de diméthylétain et de l'eau, distribuer le mélange gazeux à la surface du substrat de verre, et déposer une couche à base d'oxyde d'étain sur la surface du substrat de verre, la surface du substrat de verre étant à une température d'au moins 550 °C lorsque le mélange gazeux est délivré à ladite surface du substrat de verre.
EP23771919.0A 2022-09-06 2023-09-06 Procédé de dépôt d'une couche Pending EP4584221A1 (fr)

Applications Claiming Priority (2)

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CA1146702A (fr) * 1978-07-03 1983-05-24 Stanley M. Ohlberg Depots pyrolitiques en couche mince de cobalt/oxyde d'etain
US4571350A (en) * 1984-09-24 1986-02-18 Corning Glass Works Method for depositing thin, transparent metal oxide films
US5090985A (en) 1989-10-17 1992-02-25 Libbey-Owens-Ford Co. Method for preparing vaporized reactants for chemical vapor deposition
JP2961350B2 (ja) * 1994-08-18 1999-10-12 本荘ソレックス株式会社 微細パターンを有するネサ膜の製造方法
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