WO2017137773A1 - Procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde métallique mixte et article revêtu ainsi formé - Google Patents

Procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde métallique mixte et article revêtu ainsi formé Download PDF

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Publication number
WO2017137773A1
WO2017137773A1 PCT/GB2017/050366 GB2017050366W WO2017137773A1 WO 2017137773 A1 WO2017137773 A1 WO 2017137773A1 GB 2017050366 W GB2017050366 W GB 2017050366W WO 2017137773 A1 WO2017137773 A1 WO 2017137773A1
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Prior art keywords
metal oxide
mixed metal
vapor deposition
chemical vapor
deposition process
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PCT/GB2017/050366
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English (en)
Inventor
Srikanth Varanasi
Jun Ni
Douglas Martin NELSON
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Pilkington Group Limited
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Publication of WO2017137773A1 publication Critical patent/WO2017137773A1/fr

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    • 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
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • 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
    • C03C17/2456—Coating containing TiO2
    • 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
    • C23C16/401—Oxides containing silicon
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • 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
    • C03C2217/70—Properties of coatings
    • C03C2217/71—Photocatalytic 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
    • 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 in general to a chemical vapor deposition (CVD) process for depositing a mixed metal oxide coating.
  • the invention also relates to the mixed metal oxide coating formed according to the CVD process.
  • Forming glass articles by depositing coatings on a glass substrate is known. Also, it is known to utilize a color suppression interlayer on a glass substrate to reflect and refract light to interfere with the observance of iridescence.
  • the first coating is deposited on the glass substrate and provided with a refractive indexwhich is higher than the refractive index of the glass substrate.
  • the second coating is deposited on the first coating and is provided with a refractive index which is lower than the refractive index of the first coating and the refractive index of the glass substrate.
  • Coatings known to be utilized as the first coating in two-layer color suppression interlayers have refractive indexes that are relatively low and fail to block sodium diffusion from the glass substrate. Thus, it would be desirable to provide a coating that could be utilized as the first coating in a two-layer color suppression interlayer that has a higher refractive indexthan the known coatings and can act as a sodium diffusion barrier.
  • a color suppression interlayer that requires two coating layers adds cost and complexity to forming the glass article.
  • a color suppression interlayer with a reduced number of coating layers may be advantageous.
  • a chemical vapor deposition process for depositing a mixed metal oxide coating comprises providing a glass substrate, forming a gaseous mixture comprising a titanium-containing compound, a silicon-containing compound, and an oxygen-containing compound, and directing the gaseous mixture toward and along the glass substrate. The mixture reacts over the glass substrate to form the mixed metal oxide coating thereover.
  • the mixed metal oxide coating comprises titanium oxide and silicon oxide, wherein the mixed metal oxide coating is more than 50% titanium oxide and has a refractive index of 2.2 or less.
  • FIG. 1 is a schematic view, in vertical section, of an installation for practicing the float glass manufacturing process in accordance with certain embodiments of the invention
  • FIG. 2 is a sectional view of a coated glass article in accordance with an embodiment of the invention.
  • FIG. 3 is a sectional view of a coated glass article in accordance with another embodiment of the invention.
  • FIG. 4 is a sectional view of a coated glass article in accordance with yet another embodiment of the invention.
  • FIG. 5 is a sectional view of a coated glass article in accordance with still another embodiment of the invention.
  • a CVD process for depositing a mixed metal oxide coating (hereinafter also referred to as the "CVD process") is provided.
  • the CVD process will be described in connection with embodiments of a coated glass article 6, 6A, 6B, 6C.
  • the embodiments of the coated glass article 6, 6A, 6B, 6C may be utilized in architectural glazings, electronics, and/or have automotive, aerospace and solar cell applications.
  • the CVD process is utilized to deposit a mixed metal oxide coating 1 .
  • the mixed metal oxide coating 1 is deposited over a glass substrate 2.
  • the mixed metal oxide coating 1 comprises titanium oxide and silicon oxide.
  • the titanium oxide is titanium dioxide. More preferably, the titanium oxide is stoichiometric titanium dioxide. Titanium dioxide may be designated herein by utilizing the chemical formula Ti0 2 . However, the titanium oxide may be of another suitable stoichiometry. Also, in certain embodiments, the titanium oxide in the mixed metal oxide coating may be slightly oxygen deficient. When the titanium oxide is titanium dioxide, it is preferred that the titanium dioxide is in the anatase form. However, other forms of titanium dioxide may be present in the mixed metal oxide coating.
  • the silicon oxide is silicon dioxide. More preferably, the silicon oxide is stoichiometric silicon dioxide. Silicon dioxide may be designated herein by utilizing the chemical formula Si0 2 . However, the silicon oxide may be of another suitable stoichiometry. Also, in certain embodiments, the silicon oxide in the mixed metal oxide coating may be slightly oxygen deficient.
  • the mixed metal oxide coating comprises 2% or more silicon oxide with the balance being primarily titanium oxide, and the mixed metal oxide preferably comprising more than 50% titanium oxide.
  • the mixed metal oxide coating comprises 4% or more silicon oxide.
  • the mixed metal oxide coating comprises 10% or more silicon oxide.
  • the mixed metal oxide coating comprises 15% or more silicon oxide.
  • the mixed metal oxide coating comprises 25% or more silicon oxide.
  • the mixed metal oxide coating comprises 2 - 49% silicon oxide with the balance being primarily titanium oxide. More preferably, in these embodiments, the mixed metal oxide coating comprises 4 - 35% silicon oxide.
  • the mixed metal oxide coating may also contain contaminants of, for example, carbon, chlorine and/or fluorine. Preferably, when the mixed metal oxide coating contains contaminants, the contaminants are provided in only trace amounts or less.
  • the coating exhibits photoactivity. It should be appreciated that photoactivity refers to the mixed metal oxide coating's ability to structurally degrade dirt and other organics present on the coating when the coating is exposed to ultraviolet radiation, and subsequently washed away by water. Also, as discussed herein, photoactivity will be described with reference to the mixed metal oxide coating's ability to degrade the chemical methylene blue.
  • the photoactivity of the mixed metal oxide coating is 500 nmol/(cm 2 xhr) or more. More preferably, the mixed metal oxide coating is 1 ,000 nmol/(cm 2 xhr) or more. In other embodiments, the mixed metal oxide coating is also hydrophilic.
  • the mixed metal oxide coating 1 can be formed directly on a deposition surface 3 of the glass substrate 2 without the need to deposit a nucleation coating layer of, for example, silica (Si0 2 ) or tin oxide (Sn0 2 ) prior to forming the mixed metal oxide coating.
  • the mixed metal oxide coating 1 may be formed over one or more previously deposited coating layers 4, 5.
  • the mixed metal oxide coating may be formed at a deposition rate of 5.0 nanometers per second (nm/sec) or more. More preferably, the mixed metal oxide coating is formed at a deposition rate of 10.0 nm/sec or more. In certain embodiments, the coating is formed at a dynamic deposition rate of 225 nm x m/min or more. In these embodiments, the mixed metal oxide coating can be formed directly on the deposition surface of a glass substrate or on a coating that has been previously deposited on the glass substrate.
  • the CVD process also provides additional advantageous features.
  • the CVD process allows for the deposition of a coating layer that can be utilized in a color suppression interlayer.
  • the mixed metal oxide coating is utilized in a two-layer color suppression interlayer.
  • the mixed metal oxide coating is deposited directly on the deposition surface of the glass substrate. In this position, the coating may act as a barrier against sodium diffusion from the glass substrate.
  • the coating can be deposited so that it has a refractive index of 1.85 or more. It should be appreciated that, if the first coating layer in a two-layer color suppression interlayer has a refractive index of 1 .85 or more, the color suppression interlayer may have improved iridescence interference properties.
  • the mixed metal oxide coating may be deposited to provide a single layer color suppression interlayer. It should be appreciated that a single layer color suppression interlayer reduces the complexity and the cost required to deposit a color suppression interlayer when compared to an interlayer requiring two coating layers. In embodiments where the mixed metal oxide coating is utilized as a single layer color suppression interlayer, the mixed metal oxide coating is also deposited directly on the deposition surface of the glass substrate.
  • the CVD process comprises providing the glass substrate.
  • the glass substrate comprises the deposition surface over which the mixed metal oxide coating is formed.
  • the glass substrate is a soda-lime-silica glass.
  • the CVD process is not limited to a soda-lime- silica glass substrate as, in other embodiments, the glass substrate may be a borosilicate glass. Additionally, it may be preferable to utilize a glass substrate having a low iron content in practicing the process. Thus, in certain embodiments, the CVD process is not limited to a particular substrate composition.
  • the glass substrate is substantially transparent.
  • the invention is not limited to transparent glass substrates as translucent glass substrates may also be utilized in practicing the CVD process.
  • the transparency or absorption characteristics of the substrate may vary between embodiments.
  • the CVD process can be practiced utilizing a clear or a colored glass substrate and is not limited to a particular glass substrate thickness.
  • the CVD process may be carried out in conjunction with the manufacture of the glass substrate.
  • the glass substrate may be formed utilizing the well-known float glass manufacturing process.
  • An example of a float glass manufacturing process is illustrated in FIG. 1 .
  • the glass substrate may also be referred to as a glass ribbon.
  • the CVD process can be utilized apart from the float glass manufacturing process or well after formation and cutting of the glass ribbon.
  • the CVD process is a dynamic deposition process.
  • the glass substrate is moving at the time of forming the mixed metal oxide coating.
  • the glass substrate moves at a predetermined rate of, for example, greater than 3.175 m/min (125 in/min) as the mixed metal oxide coating is being formed thereon.
  • the glass substrate is moving at a rate of between 3.175 m/min (125 in/min) and 12.7 m/min (600 in/min) as the mixed metal oxide coating is being formed.
  • the glass substrate is heated. In an embodiment, the temperature of the glass substrate is about 1100°F (593°C) or more when the mixed metal oxide coating is deposited thereover or thereon. In another embodiment, the temperature of the glass substrate is between about 1 100°F (593°C) and 1400°F (760°C).
  • the mixed metal oxide coating is deposited over the deposition surface of the glass substrate while the surface is at essentially atmospheric pressure.
  • the CVD process is an atmospheric pressure CVD (APCVD) process.
  • APCVD atmospheric pressure CVD
  • the CVD process is not limited to being an APCVD process as, in other embodiments, the mixed metal oxide coating may be formed under low-pressure conditions.
  • the CVD process may comprise providing a source of a titanium-containing compound, a source of a silicon-containing compound, a source of one or more oxygen-containing compounds, and a source of one or more inert gases. Preferably, these sources are provided at a location outside the float bath chamber. Separate supply lines may extend from the sources of reactant (precursor) compounds and the one or more carrier gases. As used herein, the phrases "reactant compound” and "precursor compound” may be used interchangeably to refer any or all of the titanium-containing compound, silicon-containing compound, oxygen-containing compounds, and/or used to describe the various embodiments thereof disclosed herein.
  • the CVD process also comprises forming a gaseous mixture.
  • the precursor compounds suitable for use in the gaseous mixture should be suitable for use in a CVD process. Such compounds may at some point be a liquid or a solid but are volatile such that they can be vaporized for use in the gaseous mixture.
  • the gaseous mixture includes precursor compounds suitable for forming the mixed metal oxide coating at essentially atmospheric pressure. Once in a gaseous state, the precursor compounds can be included in a gaseous stream and utilized in the CVD process to form the mixed metal oxide coating.
  • the gaseous mixture comprises the titanium-containing compound, the silicon-containing compound, and an oxygen-containing compound.
  • the titanium-containing compound is an inorganic titanium-containing compound.
  • the titanium-containing compound is an inorganic, halogenated titanium-containing compound.
  • An example of an inorganic, halogenated titanium- containing compound suitable for use in the forming the gaseous mixture is titanium tetrachloride
  • Titanium tetrachloride is preferred because it is relatively inexpensive and it does not include carbon, which can become trapped in the mixed metal oxide coating during formation of the coating.
  • the invention is not limited to titanium tetrachloride as other halogenated titanium- containing compounds may be suitable for use in practicing the CVD process.
  • the titanium-containing compound is an organic titanium-containing compound.
  • the titanium-containing compound is a titanium alkoxide compound.
  • An example of a titanium alkoxide compound suitable for use in the forming the gaseous mixture is titanium isopropoxide Ti[OCH(CH 3 ) 2 ]4.
  • Another example of a titanium alkoxide compound suitable for use in the forming the gaseous mixture is titanium ethoxide Ti(OEt) 4 .
  • the invention is not limited to titanium isopropoxide and titanium ethoxide as other organic titanium- containing compounds may be suitable for use in practicing the CVD process.
  • the silicon-containing compound is a silane compound.
  • the silane compound is monosilane (SiH 4 ).
  • other silane compounds are suitable for use in practicing the CVD process.
  • disilane (Si 2 H 6 ) is a suitable silane compound for use in the CVD process.
  • Silane compounds may be pyrophoric and when oxygen-containing compounds alone are mixed with a pyrophoric silane compound, silica is produced, but it is produced at unacceptably high rates, resulting in an explosive reaction.
  • a radical scavenger it is known in the art to utilize a radical scavenger.
  • the presence of the radical scavenger allows the silane compound to be mixed with oxygen-containing compounds without undergoing ignition and premature reaction at the operating temperatures of the process.
  • such a radical scavenger is not required by the CVD process. Thus, the cost and complexity to deposit the silicon oxide portion of the mixed metal oxide coating is reduced in the CVD process.
  • the gaseous mixture comprises an oxygen-containing compound.
  • the oxygen-containing compound is an oxygen-containing organic compound such as, for example, a carbonyl compound.
  • the carbonyl compound is an ester. More preferably, the carbonyl compound is an ester having an alkyl group with a ⁇ hydrogen. Alkyl groups with a ⁇ hydrogen containing two to ten carbon atoms are preferred.
  • the ester is ethyl acetate (EtoAc). However, in other embodiments, the ester is one of ethyl formate, ethyl propionate, isopropyl formate, isopropyl acetate, n-butyl acetate or t-butyl acetate.
  • the ratio of ethyl acetate to titanium tetrachloride in the gaseous mixture is from 1 :1 to 5:1 .
  • the ratio of ethyl acetate to titanium tetrachloride in the gaseous mixture is from 1 .5:1 to 3:1 . More preferably, the ratio of ethyl acetate to titanium tetrachloride in the gaseous mixture is about 2:1 to 2.5:1 .
  • the precursor compounds are mixed to form the gaseous mixture.
  • the precursor compounds are mixed and maintained at a temperature to avoid premature reaction.
  • undesirable powder may form in the coating apparatus or on the glass substrate.
  • the CVD process can be operated for an extended period of time without the formation of undesirable powder which further reduces the cost and complexity to produce the mixed metal oxide coating.
  • the gaseous mixture may also comprise one or more inert gases utilized as carrier or diluent gas.
  • Suitable inert gases include nitrogen (N 2 ), helium (He) and mixtures thereof.
  • the CVD process may comprise providing a source of the one or more inert gases from which separate supply lines may extend.
  • the gaseous mixture is delivered to a coating apparatus.
  • the gaseous mixture is fed through a coating apparatus prior to forming the mixed metal oxide coating and discharged from the coating apparatus utilizing one or more gas distributor beams.
  • coating apparatuses suitable for being utilized in the CVD process can be found in published U.S. patent application no. 2012/0240627 and U.S. patent no. 4,922,853, the entire disclosures of which are hereby incorporated by reference.
  • the gaseous mixture is formed prior to being fed through the coating apparatus.
  • the precursor compounds may be mixed in a feed line connected to an inlet of the coating apparatus.
  • the gaseous mixture may be formed within the coating apparatus.
  • the gaseous mixture exits the coating apparatus and is directed toward and along the glass substrate. Utilizing a coating apparatus aids in directing the gaseous mixture toward and along the glass substrate.
  • the gaseous mixture is directed toward and along the glass substrate in a laminar flow.
  • the coating apparatus extends transversely across the glass substrate and is provided at a predetermined distance thereabove.
  • the coating apparatus is preferably located at a predetermined location.
  • the coating apparatus is preferably provided within the float bath section thereof.
  • the coating apparatus may be provided in the annealing lehr or in the gap between the float bath and the annealing lehr.
  • the gaseous mixture reacts at or near the deposition surface of the glass substrate to form the mixed metal oxide coating thereover.
  • the CVD process results in the deposition of a high quality coating on the glass substrate.
  • the mixed metal oxide coating formed using the CVD process exhibits excellent coating thickness uniformity.
  • the mixed metal oxide coating is a pyrolytic coating.
  • the coating By providing a mixed metal oxide coating which comprises titanium oxide and silicon oxide, the coating has a refractive index which is lower than the refractive index of a coating containing only titanium oxide.
  • Providing the mixed metal oxide coating with a refractive index as described allows the coating to be utilized as a color suppression interlayer when the coating is used in, for example, combination with other coating layers or a particular application like an architectural glazing.
  • the mixed metal oxide coating has a refractive index of 2.2 or less.
  • the mixed metal oxide coating has a refractive index of 2.15 or less. More preferably, the mixed metal oxide coating has a refractive index of 2.0 or less.
  • the refractive index can be selected by providing a desired ratio of silicon oxide to titanium oxide in the mixed metal oxide coating.
  • the refractive index of the mixed metal oxide coating may be 1 .5 to 2.2.
  • the refractive index of the mixed metal oxide coating is 1.6 to 2.1 .
  • the mixed metal oxide coating has a refractive index from 1 .85 to 2.1 .
  • the present invention provides a coated glass article comprising a glass substrate and a mixed metal oxide coating formed over the glass substrate, the mixed metal oxide coating comprising titanium oxide and silicon oxide, wherein the mixed metal oxide coating is more than 50% titanium oxide and has a refractive index of 2.2 or less.
  • the mixed metal oxide coating is comprised of 2 to 49% silicon oxide. More preferably the mixed metal oxide coating is comprised of 4 to 35% silicon oxide.
  • the mixed metal oxide coating has a refractive index of 1 .5 to 2.2. More preferably the mixed metal oxide coating has a refractive index of 1 .6 to 2.1 . Even more preferably the mixed metal oxide coating has a refractive index of 1 .85 to 2.1 .
  • the mixed metal oxide coating is formed directly on the glass substrate.
  • the mixed metal oxide exhibits photoactivity.
  • the photoactivity of the mixed metal oxide coating is 500 nmol/(cm 2 xhr) or more.
  • the mixed metal oxide coating is a pyrolytic coating.
  • the mixed metal oxide coating 1 is formed directly on the glass substrate 2.
  • the glass substrate 2 is uncoated at the time of depositing the mixed metal oxide coating 1 .
  • the mixed metal oxide coating 1 may be formed over one or more previously deposited coating layers 4, 5.
  • the previously deposited coating layer(s) may be formed in conjunction with the float glass manufacturing process or as part of another manufacturing process and may be formed by pyrolysis or by another coating deposition process, and/or by utilizing one or more additional coating apparatuses.
  • the CVD process described herein may be utilized in combination with one or more additional coating layers 7, 7A, 7B formed over the mixed metal oxide coating 1 to achieve a desired coating stack.
  • the additional coating layer(s) 7, 7A, 7B may be formed in conjunction with the float glass manufacturing process shortly after forming the mixed metal oxide coating 1 or as part of another manufacturing process.
  • these additional coating layers may be formed by pyrolysis or by another coating deposition process, and/or by utilizing one or more additional coating apparatuses.
  • the CVD process may be carried out in conjunction with the manufacture of the glass substrate in the well-known float glass manufacturing process.
  • the float glass manufacturing process is typically carried out utilizing a float glass installation such as the installation 10 depicted in the FIG. 1 .
  • the float glass installation 10 described herein is only illustrative of such installations.
  • the float glass installation 10 may comprise a canal section 20 along which molten glass 19 is delivered from a melting furnace, to a float bath section 1 1 wherein the glass substrate is formed.
  • the glass substrate will be referred to as a glass ribbon 8.
  • the glass ribbon 8 is a preferable substrate on which the mixed metal oxide coating is deposited.
  • the glass substrate is not limited to being a glass ribbon.
  • the glass ribbon 8 advances from the bath section 1 1 through an adjacent annealing lehr 12 and a cooling section 13.
  • the float bath section 1 1 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 non-oxidizing atmosphere is maintained to prevent oxidation of the molten tin 15.
  • the molten glass 19 flows along the canal 20 beneath a regulating tweel 21 and downwardly onto the surface of the tin bath 15 in controlled amounts.
  • 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 1 1 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 the mixed metal oxide coating 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 1 1 and the annealing lehr 12, or in the annealing lehr 12. Also, as illustrated in the FIG. 1 , the coating apparatus 9 is shown within the float bath section 11 .
  • the mixed metal oxide coating may be formed utilizing one coating apparatus 9 or a plurality of coating apparatuses.
  • a suitable non-oxidizing atmosphere generally nitrogen or a mixture of nitrogen and hydrogen in which nitrogen predominates, is maintained in the float bath section 11 to prevent oxidation of the molten tin 15 comprising the float bath.
  • the glass ribbon is surrounded by float bath atmosphere.
  • 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.
  • the mixed metal oxide coating is preferably formed at essentially atmospheric pressure.
  • the pressure of the float bath section 1 1 , annealing lehr 12, and/or in the gap 28 between the float bath 1 1 and 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.
  • ambient air may be directed against the glass ribbon 8 as by fans 26 in the cooling section 13.
  • Heaters (not depicted) may also be provided within the annealing lehr 12 for causing the temperature of the glass ribbon 8 to be gradually reduced in accordance with a predetermined regime as it is conveyed therethrough.
  • a soda-lime-silica glass substrate was utilized in examples Ex 1 - Ex 4 and C1 .
  • the glass substrate utilized in each of Ex 1 - Ex 4 and C1 was moving and formed in conjunction with the float glass manufacturing process.
  • the deposition surface of the glass substrate was at essentially atmospheric pressure when the coatings were deposited.
  • a silica coating was deposited on the glass substrate prior to forming the coatings thereover.
  • the resulting coated glass articles of Ex 1 - Ex 4 are of a glass/silica/mixed metal oxide arrangement.
  • the resulting coated glass article of C1 is of a glass/silica/titanium oxide arrangement.
  • a gaseous mixture comprising certain precursor compounds was formed for each of Ex 1 - Ex 4 and C1 .
  • the gaseous mixtures comprised titanium tetrachloride, monosilane, and ethyl acetate.
  • the gaseous mixture comprised titanium tetrachloride and ethyl acetate.
  • the flow rates for the titanium tetrachloride and monosilane are as listed in TABLE 1 .
  • the gaseous mixtures utilized for Ex 1 - Ex 4 and C1 also comprised inert gases.
  • the line speed for Ex 1 - Ex 4 and C1 i.e. the speed of the glass substrate moving beneath the coating apparatus from which the gaseous precursor compounds were delivered, was 10.19 m/min.
  • the ratio of titanium oxide to silicon oxide in each coating was determined using an XPS technique and is reported in TABLE 1 . Also, the form of the titanium dioxide in each coating is reported in TABLE 1 . The thickness of each coating deposited according to Ex 1 - Ex 4 and C1 is reported in TABLE 1 . The coating thicknesses reported in TABLE 1 were determined using a scanning electron microscope (SEM) and are reported in nanometers (nm). Also, the dynamic deposition rate (DDR) of each coating is reported in TABLE 1 . It should be appreciated that DDR refers to the thickness of the coating multiplied by the line speed in meters per minute (m/min). The DDR is useful for comparing coating deposition rates at different line speeds.
  • each coating is reported in TABLE 1 .
  • the refractive index of each coating at 550 nanometers (nm) deposited according to Ex 1 - Ex 4 and C1 is also listed in Table 1 .
  • the refractive indices were calculated by optical modeling.
  • the photoactivity of the mixed metal oxide coatings of Ex 1 - Ex 4 and the titanium oxide coating of C1 are listed in TABLE 1 .
  • the photoactivity of the mixed metal oxide coatings of Ex 1 - Ex 4 and the titanium oxide coating of C1 were measured utilizing the chemical methylene blue and after exposing the coatings to ultraviolet radiation.
  • a mixed metal oxide coating comprising titanium oxide and silicon oxide can be deposited on a glass substrate.
  • the mixed metal oxide coating can be formed at a deposition rate of more than 5.0 nm/sec.
  • the mixed metal oxide coatings of Ex 1 - Ex 4 were all formed at a deposition rate of about 10 nm/sec or more.
  • the mixed metal oxide coatings of Ex 1 - Ex 4 were all formed at a DDR of more than 225 nm x m/min.
  • the mixed metal oxide coatings of Ex 1 - Ex 4 have refractive indices which are lower than the refractive index of the titanium oxide coating of C1 .
  • the mixed metal oxide coatings of Ex 1 - Ex 4 all exhibited refractive indices of more than 1 .85. In fact, the mixed metal oxide coatings of Ex 1 - Ex 4 all exhibited refractive indices of 1 .98 or more.
  • the photoactivities of the mixed metal oxide coatings of Ex 1 - Ex 4 were all greater than 500 nmol/(cm 2 xhr). More advantageously, the mixed metal oxide coating of Ex 1 exhibited a photoactivity of more than 1 ,000 nmol/(cm 2 xhr).

Abstract

La présente invention concerne un procédé de dépôt chimique en phase vapeur qui permet de déposer un revêtement d'oxyde métallique mixte. L'invention concerne également un revêtement d'oxyde métallique mixte formé par ledit procédé de dépôt chimique en phase vapeur.
PCT/GB2017/050366 2016-02-12 2017-02-10 Procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde métallique mixte et article revêtu ainsi formé WO2017137773A1 (fr)

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EP0309902A2 (fr) * 1987-09-30 1989-04-05 Ppg Industries, Inc. Dépôt chimique en phase vapeur d'oxyde d'étain sur du verre flotté dans le bain d'étain
US4922853A (en) 1989-05-16 1990-05-08 Libbey-Owens-Ford Co. Stripe coating on glass by chemical vapor deposition
EP0611733A2 (fr) * 1993-02-16 1994-08-24 Ppg Industries, Inc. Appareil et procédé pour le revêtement de verre, composés et compositions pour le revêtement de verre et substrats en verre revêtus
EP0879802A2 (fr) * 1997-05-23 1998-11-25 Pilkington Plc Procédé de revêtement
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US20100124643A1 (en) * 2008-11-19 2010-05-20 Ppg Industries Ohio, Inc. Undercoating layers providing improved photoactive topcoat functionality
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US20120240627A1 (en) 2011-03-23 2012-09-27 Pilkington Group Limited Apparatus for depositing thin film coatings and method of deposition utilizing such apparatus
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EP0309902A2 (fr) * 1987-09-30 1989-04-05 Ppg Industries, Inc. Dépôt chimique en phase vapeur d'oxyde d'étain sur du verre flotté dans le bain d'étain
US4922853A (en) 1989-05-16 1990-05-08 Libbey-Owens-Ford Co. Stripe coating on glass by chemical vapor deposition
EP0611733A2 (fr) * 1993-02-16 1994-08-24 Ppg Industries, Inc. Appareil et procédé pour le revêtement de verre, composés et compositions pour le revêtement de verre et substrats en verre revêtus
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EP0879802A2 (fr) * 1997-05-23 1998-11-25 Pilkington Plc Procédé de revêtement
WO2009136201A1 (fr) * 2008-05-08 2009-11-12 Pilkington Group Limited Fabrication de verre enduit
US20100124643A1 (en) * 2008-11-19 2010-05-20 Ppg Industries Ohio, Inc. Undercoating layers providing improved photoactive topcoat functionality
EP2192091A1 (fr) * 2008-12-01 2010-06-02 ETH Zurich Procédé pour fournir des propriétés super-hydrophiles d'un substrat
US20120240627A1 (en) 2011-03-23 2012-09-27 Pilkington Group Limited Apparatus for depositing thin film coatings and method of deposition utilizing such apparatus
WO2013124634A1 (fr) * 2012-02-23 2013-08-29 Pilkington Group Limited Procédé de dépôt chimique en phase vapeur pour le dépôt d'un revêtement de silice sur un substrat de verre

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VISHWAS M ET AL: "Optical, electrical and dielectric properties of TiOSiOfilms prepared by a cost effective solgel process", SPECTROCHIMICA ACTA. PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, ELSEVIER, AMSTERDAM, NL, vol. 83, no. 1, 10 August 2011 (2011-08-10), pages 614 - 617, XP028314686, ISSN: 1386-1425, [retrieved on 20110818], DOI: 10.1016/J.SAA.2011.08.009 *

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