WO2023057756A1 - Procédé de formation d'un revêtement d'oxyde de silicium - Google Patents

Procédé de formation d'un revêtement d'oxyde de silicium Download PDF

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Publication number
WO2023057756A1
WO2023057756A1 PCT/GB2022/052522 GB2022052522W WO2023057756A1 WO 2023057756 A1 WO2023057756 A1 WO 2023057756A1 GB 2022052522 W GB2022052522 W GB 2022052522W WO 2023057756 A1 WO2023057756 A1 WO 2023057756A1
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WIPO (PCT)
Prior art keywords
silicon oxide
oxide coating
glass substrate
gaseous mixture
coated glass
Prior art date
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PCT/GB2022/052522
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English (en)
Inventor
Douglas Martin NELSON
Steven Edward PHILLIPS
Lila Raj DAHAL
Vikash RANJAN
Jun Ni
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Pilkington Group Limited
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Publication of WO2023057756A1 publication Critical patent/WO2023057756A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—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
    • 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
    • C23C16/455—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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/213—SiO2
    • 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

  • the subject matter of the embodiments described herein relates generally to a method of forming a silicon oxide coating and, more particularly, to a method of forming a silicon oxide coating utilizing a gaseous mixture comprising a sulfur-containing compound to enhance desired characteristics of the silicon oxide coating.
  • the invention relates to processes for producing coated substrates and to substrates having such coatings on at least one surface.
  • the invention also relates to glazings comprising such coated substrates, in particular automotive and architectural glazings.
  • Coatings on substrates may be used to modify the properties of the substrate.
  • a number of methods may be used to deposit coatings including many liquid-based methods such as spin coating, dip coating, spray coating, and various printing techniques.
  • One conventional method for depositing a coating on a substrate is chemical vapor deposition (CVD) wherein a fluid precursor in the form of a vapor is delivered to a surface of the substrate where the precursors react and/or decompose thereby depositing the coating.
  • CVD chemical vapor deposition
  • Particular types of CVD include metal organic (MO) CVD, combustion (C) CVD, plasma enhanced (PE) CVD, and aerosol-assisted (AA) CVD.
  • a chemical vapor deposition method for forming a silicon oxide coating comprises: providing a glass substrate; forming a precursor gaseous mixture comprised of a silane compound, a first oxygen-containing molecule, at least one radical scavenger, and a sulfur-containing compound; directing the precursor gaseous mixture toward and along the substrate; and reacting the precursor gaseous mixture to form a silicon oxide coating over the glass substrate.
  • a method of coating a substrate comprises: providing a glass substrate; and forming a silicon oxide coating over the substrate using a chemical vapor deposition process, wherein the chemical vapor deposition process utilizes a precursor gaseous mixture comprising a silane compound, a first oxygen-containing molecule, at least one radical scavenger, and a sulfur-containing compound, wherein the sulfur-containing compound acts as a catalyst for a reaction which forms the silicon oxide coating over the glass substrate.
  • a coated glass article comprises: a glass substrate; and a silicon oxide coating deposited on the glass substrate by a chemical vapor deposition process utilizing a silane compound, a first oxygen-containing molecule, at least one radical scavenger, and a sulfur-containing compound, wherein the sulfur-containing compound acts as a catalyst for a reaction which forms the silicon oxide coating over the glass substrate.
  • the sulfur-containing compound is dimethyl sulfoxide.
  • a temperature of the glass substrate is at least
  • a temperature of the glass substrate is between 425°C and 700°C, more preferably between 450°C and 700°C, when the precursor gaseous mixture is reacted during the chemical vapor deposition process.
  • the at least one radical scavenger is at least one of ethylene, propylene, and butene.
  • the at least one radical scavenger is ethylene.
  • the substrate comprises soda-lime-silica glass.
  • the substrate is formed by a float glass process.
  • the sulfur-containing compound is added to the precursor gaseous mixture at a rate of at least 0.9 Standard Liter Per minute (SLPM).
  • the precursor gaseous mixture is reacted over the substrate at essentially atmospheric pressure.
  • the substrate is moving when the silicon oxide coating is deposited.
  • the silicon oxide coating is an outermost layer over the glass substrate.
  • the silicon oxide coating is formed over a previously deposited layer on the glass substrate.
  • the silicon oxide coating has a thickness of at least 15 nm.
  • the silicon oxide coating has a thickness in a range of about 15 nm to about 75 nm.
  • the silicon oxide coating exhibits a refractive index of no more than 1 .4.
  • the silicon oxide coating exhibits a refractive index between about 1 .0 and about 1 .4.
  • the refractive index values described herein are reported as an average value across 400-780 nm of the electromagnetic spectrum.
  • the precursor gaseous mixture also comprises a second oxygen-containing molecule, the first oxygen-containing molecule being molecular oxygen and the second oxygen-containing molecule being water vapor.
  • the silane compound is monosilane
  • the first oxygen-containing molecule is molecular oxygen
  • the at least one radical scavenger is ethylene
  • the silicon oxide coating is pyrolytic.
  • the silane compound is monosilane.
  • FIG. 1 is a chart providing actual results for a coated glass article showing a refractive index value of a glass article having a silicon oxide coating, formed using a precursor gaseous mixture without a sulfur-containing compound, for light wavelengths in a range of about 300 nm to about 1500 nm, and a refractive index value of a glass article having a silicon oxide coating, formed using a precursor gaseous mixture comprising a sulfur- containing compound, for light wavelengths in a range of about 300 nm to about 1500 nm; and
  • FIG. 2 is a schematic view, in vertical section, of an installation for practicing a float glass manufacturing process in accordance with an embodiment of the subject matter.
  • 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.
  • 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 method for forming a silicon oxide coating according to one embodiment of the presently disclosed subject matter is a chemical vapor deposition process for forming the silicon oxide coating (hereinafter referred to as the “CVD process”).
  • coated glass article may have numerous applications across various products and industries.
  • the coated glass article may be utilized in solar cell applications, architectural glazings, electronics, and automotive and aerospace applications.
  • the silicon oxide coating comprises silicon and oxygen.
  • the silicon oxide coating may form using a sulfur-containing compound.
  • the silicon oxide coating may also include a trace amount of one or more additional constituents such as, for example, carbon.
  • trace amount is an amount of a constituent of the silicon oxide coating that is less than 0.01 weight
  • a feature of the CVD process is that it allows for the formation of silicon oxide coatings at commercially viable deposition rates. Additionally, an advantage of the CVD process is that it is more efficient than known processes for forming a silicon oxide coating. Thus, commercially viable deposition rates can be achieved using less silicon containing compound than in the known processes, which reduces the cost to form the silicon oxide coating.
  • the silicon oxide coating is formed over a substrate. It should be appreciated that the silicon oxide coating may be formed directly on the substrate or on a coating previously deposited on the substrate. In a preferable embodiment, the silicon oxide coating is formed over a glass substrate, wherein the glass substrate has a deposition surface over which the silicon oxide coating is formed. In another preferable embodiment, the silicon oxide coating is formed over a tin oxide coating deposited over the substrate. Yet, in another preferable embodiment, the silicon oxide coating is formed over a titanium dioxide coating deposited over the substrate.
  • the CVD process may be carried out in conjunction with the manufacture of the glass substrate, preferably in conjunction with the well-known float glass manufacturing process.
  • the glass substrate may be formed utilizing the float glass manufacturing process.
  • 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 silicon oxide coating.
  • the glass substrate moves at a predetermined rate of, for example, greater than 3.175 m/min (125 in/min) as the silicon oxide coating is being formed.
  • 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 silicon 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 silicon oxide coating is formed. In another embodiment, the temperature of the glass substrate is between 1100°F (593°C) and OOT (760°C) when the silicon oxide coating is formed thereon.
  • the silicon 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 silicon oxide coating may be formed under low-pressure conditions.
  • the glass substrate is not limited to a particular thickness.
  • the glass substrate is a soda-lime-silica glass.
  • the substrate may be a portion of the float glass ribbon.
  • the CVD process is not limited to a soda-lime-silica glass substrate as, in other embodiments, the glass substrate may be a borosilicate or aluminosilicate glass.
  • the transparency or absorption characteristics of the glass substrate may vary between embodiments.
  • the glass substrate may comprise 0.15 weight % Fe 2 O 3 (total iron) or less.
  • total iron refers to the total weight of iron oxide (FeO + Fe 2 O 3 ) contained in the glass. More preferably, the glass substrate comprises 0.1 weight % Fe 2 O 3 (total iron) or less, and, even more preferably, a 0.02 weight % Fe 2 O 3 (total iron) or less.
  • the glass substrate comprises 0.012 weight % Fe 2 O 3 (total iron).
  • the glass substrate may exhibit a total visible light transmittance of 91 % or more in the CIELAB color scale system (llluminant C, ten degree observer). Further, the color of the glass substrate can vary between embodiments of CVD process.
  • the glass substrate may be substantially clear. In other embodiments, the glass substrate may be tinted or colored such as bronze or gray, for example.
  • the silicon oxide coating may be deposited by providing one or more of a source of a silane compound, one or more sources of one or more oxygen-containing molecules, a source of a sulfur-containing compound, and a source of a radical scavenger.
  • a source of an oxygen-containing molecule may be a source of water.
  • Separate supply lines may extend from the sources of the reactant (precursor) molecules.
  • the phrases “reactant molecule” and “precursor molecule” may be used interchangeably to refer to any or all of the silane compound, one or more oxygen-containing molecules, radical scavenger, sulfur-containing compound, and/or used to describe the various embodiments thereof disclosed herein.
  • the sources of the precursor molecules are provided at a location outside the float bath chamber.
  • the silicon oxide coating is deposited by forming a precursor gaseous mixture.
  • the precursor molecules suitable for use in the precursor gaseous mixture are suitable for use in a CVD process. Such molecules may at some point be a liquid or a solid but are volatile such that they can be vaporized for use in the precursor gaseous mixture.
  • the precursor gaseous mixture includes precursor molecules suitable for forming the silicon oxide coating at essentially atmospheric pressure. Once in a gaseous state, the precursor molecules can be included in a gaseous stream and utilized to form the silicon oxide coating.
  • the optimum concentrations and flow rates for achieving a particular deposition rate and coating thickness may vary.
  • the gaseous mixture comprises a silane compound, one or more oxygen-containing molecules, a radical scavenger, and a sulfur-containing compound.
  • the precursor gaseous mixture comprises a sulfur-containing compound.
  • the silane compound is monosilane (SiH 4 ).
  • other silane compounds are suitable for use in depositing the silicon oxide coating.
  • disilane (Si 2 H 6 ) is another silane compound that may be utilized in depositing the silicon oxide coating.
  • one or more of the silane compound, radical scavenger, and sulfur-containing compound may comprise one or more oxygen elements.
  • the phrase “one or more oxygen-containing molecules” refers to one or more molecules included in the precursor gaseous mixture that are separate from the silane compound, radical scavenger, and the sulfur-containing compound.
  • the one or more oxygen-containing molecules comprise a first oxygen-containing molecule.
  • the first oxygen-containing molecule is molecular oxygen (O 2 ), which can be provided as a part of a gaseous composition such as air or in a substantially purified form.
  • the first oxygen-containing molecule is water (H 2 O) vapor, which may be provided as steam.
  • the one or more oxygen-containing molecules comprises two oxygen-containing molecules.
  • the precursor gaseous mixture comprises the first oxygen-containing molecule and a second oxygen-containing molecule.
  • the first oxygen-containing molecule may be molecular oxygen and the second oxygen-containing molecule may be water vapor or vice versa.
  • the precursor gaseous mixture may comprise more water vapor than molecular oxygen.
  • the ratio of molecular oxygen to water vapor in the precursor gaseous mixture may be 1 :5 or more, more preferably 1 :10 or more, even more preferably 1 :20 or more, most preferably 1 :50 or more.
  • the precursor gaseous mixture may comprise 50% or more water vapor, more preferably 60% or more water vapor, most preferably 70% or more water vapor, which may be based on mol percentage (mol%).
  • Silane compounds may be pyrophoric and when the one or more oxygen-containing molecules are added to a precursor gaseous mixture comprising a pyrophoric silane compound, a silicon oxide coating such as, for example, silica (SiO 2 ) may be produced.
  • a silicon oxide coating such as, for example, silica (SiO 2 ) may be produced.
  • the coating is produced at unacceptably high rates and an explosive reaction may result.
  • Known methods of preventing such a reaction result in the deposition of coatings at very low, commercially impractical rates.
  • Known methods are also limited in the amount of silane and oxygen which can be contained in the precursor gaseous mixture, as too high a concentration results in gas phase reaction of the elements, and no coating being produced. Therefore, it is preferred that the precursor gaseous mixture comprises a radical scavenger.
  • the radical scavenger allows the silane compound to be mixed with the one or more oxygen-containing molecules without undergoing ignition and premature reaction at the operating temperatures.
  • the radical scavenger further provides control of and permits optimization of the kinetics of the reaction above, near, and/or on the glass substrate.
  • the radical scavenger is a hydrocarbon gas.
  • the hydrocarbon gas is ethylene (C 2 H 4 ) or propylene (C 3 H 6 ), and is most preferably ethylene (C 2 H 4 ).
  • the sulfur-containing compound is an organic sulfur-containing compound.
  • the sulfur-containing compound is dimethyl sulfoxide (DMSO). It is understood that other embodiments may employ any suitable sulfur- containing compound for use in the precursor gaseous mixture as desired, e.g. the sulfur- containing compound may be one or more of DMSO, dimethyl sulfide (DMS), ethylene sulfide, propylene sulfide and ethyl thioacetate.
  • the benefits of utilizing a sulfur-containing compound, like the embodiments described above, to form the silicon oxide coating can be realized by selecting a ratio of sulfur- containing compound to silane compound in the precursor gaseous mixture.
  • the ratio of sulfur-containing compound to silane compound in the precursor gaseous mixture is between 1 :2.5 and 1 :0.35. More preferably, the ratio of sulfur-containing compound to silane compound in the precursor gaseous mixture is between 1 :2.5 and 1 :0.9.
  • the mol% of sulfur-containing compound in the precursor gaseous mixture may be less than 0.9.
  • the precursor gaseous mixture may comprise 0.45 mol% or less sulfur-containing compound.
  • the precursor gaseous mixture may comprise between 0.45 mol% and 0.9 mol% of sulfur-containing compound.
  • the silicon oxide coating may comprise a trace amount of sulfur or more. In other embodiments, the silicon oxide coating may comprise a trace amount of sulfur or less.
  • the precursor gaseous mixture may also comprise one or more inert gases utilized as carrier or diluent gas.
  • Suitable inert gases include nitrogen (N2), helium (He), and mixtures thereof.
  • sources of the one or more inert gases, from which separate supply lines may extend, may be provided.
  • the precursor molecules are mixed to form the precursor gaseous mixture.
  • the silane compound can be mixed with one or more oxygen-containing molecules without undergoing ignition and premature reaction due to the presence of the radical scavenger.
  • the sulfur-containing compound is also mixed with the silane compound, oxygen-containing molecule(s) and radical scavenger to form the precursor gaseous mixture.
  • the precursor gaseous mixture comprises a sulfur-containing compound.
  • a coating apparatus may be provided.
  • the precursor gaseous mixture is fed through the coating apparatus before forming the silicon oxide coating over the glass substrate.
  • the precursor gaseous mixture may be discharged from the coating apparatus utilizing one or more gas distributor beams.
  • the precursor gaseous mixture is formed prior to being fed through the coating apparatus.
  • the precursor molecules may be mixed in a feed line connected to an inlet of the coating apparatus.
  • the precursor gaseous mixture may be formed within the coating apparatus.
  • An advantage of the CVD process described herein is the significant increase in the deposition rate that occurs and the reduction in the amount of pre-reaction/powder formation that occurs when forming the silicon oxide coating. Hence, the CVD process can be operated for run lengths which are much greater than those of conventional processes. Depending on the thickness of the silicon oxide coating required, the coating formed by the CVD process may be deposited by forming a plurality of silicon oxide coating layers consecutively. However, depending on the desired thickness, another advantage of the CVD process is that only a single coating apparatus may be required for forming the silicon oxide coating.
  • the coating apparatus extends transversely across the glass substrate and is provided at a predetermined distance thereabove.
  • the coating apparatus is preferably located at, at least, one predetermined location.
  • the coating apparatus is preferably provided within the float bath section thereof.
  • the coating apparatus may be provided in the annealing lehr, and/or in the gap between the float bath and the annealing lehr.
  • the precursor gaseous mixture is directed toward and along the glass substrate.
  • Utilizing a coating apparatus aids in directing the precursor gaseous mixture toward and along the glass substrate.
  • the precursor gaseous mixture is directed toward and along the glass substrate in a laminar flow.
  • the precursor gaseous mixture reacts at or near the glass substrate to form the silicon oxide coating thereover.
  • the precursor gaseous mixture comprises a silane compound, a first oxygen-containing molecule, and a radical scavenger.
  • the silane compound is monosilane
  • the first oxygen-containing molecule is molecular oxygen
  • the radical scavenger is ethylene.
  • the precursor gaseous mixture comprises a second oxygen-containing molecule such as, for example, water vapor and a sulfur-containing compound
  • the silicon oxide coating may be formed as the glass substrate is moving and at a deposition rate of about 12 nm/second resulting in the silicon oxide coating having an optical thickness of about 50 nm.
  • the silicon oxide coating may be formed as the glass substrate is moving and at a deposition rate of about 18 nm/second resulting in the silicon oxide coating having an optical thickness of about 75 nm.
  • the silicon oxide coating may be deposited at a rate greater than 4 nm/second and may have an optical thickness of at least 15 nm. In other certain embodiments, the silicon oxide coating may be deposited at a rate of about 6 nm/second or more and may have an optical thickness of about 25 nm to about 75 nm. Preferably, the optical thickness of the silicon oxide coating is in a range of about 15 nm to about 75 nm.
  • the silicon oxide coating may exhibit excellent coating thickness uniformity.
  • the silicon oxide coating is pyrolytic.
  • the term “pyrolytic” may refer to a coating that is chemically bonded to a glass substrate.
  • the silicon oxide coating exhibits a refractive index between about 1.0 and about 1.4, and more preferably, between about 1.25 and about 1.4. Accordingly, the silicon oxide coating formed using the sulfur-containing compound in the precursor gaseous mixture may reduce the refractive index of the silicon oxide coating. It is believed that such reduction in the refractive index of the silicon oxide coating may be due to an increase in a porosity of the silicon dioxide coating.
  • a comparative example includes a mid-iron, soda-lime-silica glass substrate with a silicon oxide coating formed without using the sulfur-containing compound.
  • a float glass manufacturing process was employed with the glass substrate moving at a line speed of about 572 cm/min (225 in. /min.) and having a temperature of about 649°C (1200°F) at a time the silicon oxide coating was deposited thereon.
  • a precursor gaseous mixture of a “water-in” silica (WIS) chemistry formed by monosilane (SiH 4 ) at a rate of 2 L/min, ethylene (C 2 H 4 ) at a rate of 12 L/min, oxygen (O 2 ) at a rate of 20 L/min, and water (H 2 O) at a rate of 400 cc/min was reacted over the glass substrate which resulted in a silicon oxide coating deposited at a rate of about 4 to about 5 nm/second having an optical thickness of about 20 to about 25 nm and a refractive index that is in a range of about 1 .40 to about 1.55 across 300-1500 nm of the electromagnetic spectrum, as shown in FIG. 1.
  • WIS water-in silica
  • An example within the scope of the presently described subject matter includes a midiron, soda-lime-silica glass substrate with a silicon oxide coating formed using the sulfur- containing compound.
  • a float glass manufacturing process was employed with the glass substrate moving at a line speed of about 572 cm/min (225 in. /min.) and having a temperature of about 649°C (1200°F) at a time the silicon oxide coating was deposited thereon.
  • the silicon oxide coating may be formed over one or more previously deposited coatings.
  • the silicon oxide coating may be formed over a previously deposited tin oxide coating or titanium dioxide coating, which was formed over the deposition surface of the glass substrate.
  • the tin oxide coating or the titanium dioxide coating, over which the silicon oxide coating is to be deposited may be doped with fluorine or deposited directly on the glass substrate.
  • the silicon oxide coating may be formed directly on the tin oxide coating or the titanium dioxide coating.
  • the silicon oxide coating may be formed directly on the glass substrate. In this position, the silicon oxide coating may act as a sodium diffusion barrier between the glass substrate and any coatings formed over the silicon oxide coating. This may be particularly advantageous when the glass substrate is a soda-lime-silica glass.
  • the silicon oxide coating may be formed 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 30 depicted in FIG. 2.
  • a float glass installation such as the installation 30 depicted in FIG. 2.
  • the float glass installation 30 described herein is only illustrative of such installations.
  • the float glass installation 30 may comprise a canal section 32 along which molten glass 34 is delivered from a melting furnace, to a float bath section 36 where the glass substrate is formed.
  • the glass substrate will be referred to as a glass ribbon 38.
  • the glass ribbon 38 is a preferable substrate on which the silicon oxide coating is formed.
  • the glass substrate is not limited to being a glass ribbon.
  • the glass ribbon 38 advances from the bath section 36 through an adjacent annealing lehr 40 and a cooling section 42.
  • the float bath section 36 includes: a bottom section 44 within which a bath of molten tin 46 is contained, a roof 48, opposite side walls (not depicted) and end walls 50, 52.
  • the roof 48, side walls and end walls 50, 52 together define an enclosure 54 in which a non-oxidizing atmosphere is maintained to prevent oxidation of the molten tin 46.
  • the molten glass 34 flows along the canal 32 beneath a regulating tweel 56 and downwardly onto the surface of the tin bath 46 in controlled amounts.
  • the molten glass 34 spreads laterally under the influence of gravity and surface tension, as well as certain mechanical influences, and it is advanced across the tin bath 46 to form the glass ribbon 38.
  • the glass ribbon 38 is removed from the bath section 36 over lift out rolls 58 and is thereafter conveyed through the annealing lehr 40 and the cooling section 42 on aligned rolls.
  • the deposition of the silicon oxide coating preferably takes place in the float bath section 36, although it may be possible for deposition to take place further along the glass production line, for example, in the gap 60 between the float bath 36 and the annealing lehr 40, or in the annealing lehr 40.
  • a coating apparatus 62 is shown within the float bath section 36.
  • the silicon oxide coating may be formed utilizing the coating apparatus 62.
  • the silicon oxide coating may be formed directly on the glass substrate.
  • the silicon oxide coating may be formed over one or more coatings previously formed on the glass ribbon 38. Each of these coatings may be formed utilizing a separate coating apparatus.
  • a coating layer comprising undoped tin oxide may be deposited utilizing a coating apparatus 62, 64.
  • a coating layer comprising undoped titanium dioxide may be deposited utilizing the coating apparatus 62, 64.
  • the silicon oxide coating may be formed directly on or over the undoped tin oxide coating or the undoped titanium dioxide coating utilizing another coating apparatus 64-68, which is positioned downstream of the coating apparatus 62, 64 utilized to form the undoped tin oxide coating or the undoped titanium dioxide coating, provided in the float bath section 36 or in another portion of the float glass installation 30 as described above.
  • a coating apparatus 66 may be provided and utilized to form a coating that comprises either fluorine doped tin oxide or fluorine doped titanium dioxide.
  • the silicon oxide coating may be formed directly on or over the doped tin oxide coating or the doped titanium dioxide utilizing a coating apparatus 68 positioned downstream of the coating apparatus 66.
  • 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 36 to prevent oxidation of the molten tin 46 comprising the float bath.
  • the atmosphere gas is admitted through conduits 70 operably coupled to a distribution manifold 72.
  • 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 silicon oxide coating is formed at essentially atmospheric pressure.
  • the pressure of the float bath section 36, annealing lehr 40, and/or in the gap 60 between the float bath section 36 and the annealing lehr 40 may be essentially atmospheric pressure.
  • Heat for maintaining the desired temperature regime in the float bath section 36 and the enclosure 54 is provided by radiant heaters 74 within the enclosure 54.
  • the atmosphere within the lehr 40 is typically atmospheric air, as the cooling section 42 is not enclosed and the glass ribbon 38 is therefore open to the ambient atmosphere.
  • the glass ribbon 38 is subsequently allowed to cool to ambient temperature.
  • ambient air may be directed against the glass ribbon 38 as by fans 76 in the cooling section 42.
  • Heaters (not depicted) may also be provided within the annealing lehr 40 for causing the temperature of the glass ribbon 38 to be gradually reduced in accordance with a predetermined regime as it is conveyed therethrough.

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

Abstract

Un procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde de silicium qui comprend la fourniture d'un substrat de verre en déplacement. Un mélange gazeux précurseur est formé et comprend un composé silane, une première molécule contenant de l'oxygène, au moins un piégeur de radicaux et un composé soufré. Le mélange gazeux précurseur est dirigé vers le substrat de verre et le long de ce dernier. Le mélange gazeux précurseur est mis à réagir pour former un revêtement d'oxyde de silicium sur le substrat de verre.
PCT/GB2022/052522 2021-10-06 2022-10-06 Procédé de formation d'un revêtement d'oxyde de silicium WO2023057756A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5599387A (en) * 1993-02-16 1997-02-04 Ppg Industries, Inc. Compounds and compositions for coating glass with silicon oxide
US5798142A (en) * 1994-10-14 1998-08-25 Libbey-Owens-Ford Co. CVD method of depositing a silica coating on a heated glass substrate
EP0879802A2 (fr) * 1997-05-23 1998-11-25 Pilkington Plc Procédé de revêtement
US20050044894A1 (en) * 2003-08-29 2005-03-03 Douglas Nelson Deposition of silica coatings on a substrate
US20150140216A1 (en) * 2012-02-23 2015-05-21 Pilkington Group Limited Chemical vapor deposition process for depositing a silica coating on a glass substrate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5599387A (en) * 1993-02-16 1997-02-04 Ppg Industries, Inc. Compounds and compositions for coating glass with silicon oxide
US5798142A (en) * 1994-10-14 1998-08-25 Libbey-Owens-Ford Co. CVD method of depositing a silica coating on a heated glass substrate
EP0879802A2 (fr) * 1997-05-23 1998-11-25 Pilkington Plc Procédé de revêtement
US20050044894A1 (en) * 2003-08-29 2005-03-03 Douglas Nelson Deposition of silica coatings on a substrate
US20150140216A1 (en) * 2012-02-23 2015-05-21 Pilkington Group Limited Chemical vapor deposition process for depositing a silica coating on a glass substrate

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