WO2016132131A1 - Procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde d'étain dopé au fer, et article de verre revêtu ainsi obtenu - Google Patents

Procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde d'étain dopé au fer, et article de verre revêtu ainsi obtenu Download PDF

Info

Publication number
WO2016132131A1
WO2016132131A1 PCT/GB2016/050401 GB2016050401W WO2016132131A1 WO 2016132131 A1 WO2016132131 A1 WO 2016132131A1 GB 2016050401 W GB2016050401 W GB 2016050401W WO 2016132131 A1 WO2016132131 A1 WO 2016132131A1
Authority
WO
WIPO (PCT)
Prior art keywords
tin oxide
oxide coating
doped tin
glass
glass substrate
Prior art date
Application number
PCT/GB2016/050401
Other languages
English (en)
Inventor
Srikanth Varanasi
Lila Raj DAHAL
Vikash RANJAN
Michel Jean SOUBEYRAND
Original Assignee
Pilkington Group Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pilkington Group Limited filed Critical Pilkington Group Limited
Publication of WO2016132131A1 publication Critical patent/WO2016132131A1/fr

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
    • C03C17/001—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
    • C03C17/2453—Coating containing SnO2
    • 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
    • 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
    • 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
    • C03C2217/24—Doped oxides
    • 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 vapour deposition (CVD) process and a coated glass article formed thereby.
  • this invention relates to a CVD process for depositing an iron doped tin oxide coating and a glass article having an iron doped tin oxide coating formed thereon.
  • Tin oxide coatings are known to be deposited over glass substrates. It is also known to decrease the resistivity of a tin oxide coating by doping the coating with a material such as, for example, fluorine.
  • WO200172652A1 LEF/Varanasi
  • WO200172652A1 concerns a tin oxide coating having at least one dopant. Fluorine as a dopant is believed to substitute for oxygen thereby decreasing the sheet resistance.
  • Niobium as a dopant is believed to substitute for tin, also decreasing sheet resistance. A combination of fluorine and niobium dopants also decreases sheet resistance.
  • EP1624494A1 A combination of fluorine and niobium dopants also decreases sheet resistance.
  • EP1624494A1 ATC/Fukawa discloses a transparent conductive substrate for a solar cell comprising a layer of tin oxide doped with a substance for exhibiting conductivity.
  • Tin oxide coatings are also known in a flat screen video display. Such a video display is designed to be less obtrusive when the display is not in operation. One way to accomplish this objective is to conceal the video display by giving it the appearance of an object that might commonly appear in a room, such as a mirror.
  • a known product for such an application is sold by Pilkington North America, Inc. as Pilkington MirroviewTM. This product includes a clear glass substrate provided with a coating stack formed of a layer of silicon on the glass, a layer of silica on the layer of silicon, and a layer of tin oxide on the layer of silica, providing a visible light transmittance (Tvis) of about 20% and a film side reflectance (Rf) of 70-75%.
  • Tvis visible light transmittance
  • Rf film side reflectance
  • WO 2015121632 discloses a coated glass article that has a mirror-like appearance for concealing a video display when the display is not in use.
  • the coated glass article permits a video image from the display to be bright and sharp when the display is in use and utilized in areas with high levels of natural light.
  • the coating comprises an optional base layer of an oxide of silicon deposited over a major surface of the glass substrate, a first coating layer of an oxide of titanium, niobium or chromium deposited over the optional base layer, a second coating layer of an oxide of silicon deposited over the first coating layer, and a third coating layer of an oxide of tin deposited over the second coating layer.
  • the coated glass article exhibits a Tvis of 40% - 55% and an Rf of 40% - 60%.
  • a predetermined resistivity for such a coated glass article for example to discharge an amount of static electricity which may occur during cleaning. It may be desirable that he coated glass article should have approximately similar Tvis to Pilkington MlrroviewTM.
  • a process of manufacture of a glass article comprising the steps set out in claim 1.
  • the chemical vapour deposition process for forming a coated glass article comprises steps: providing a glass substrate;
  • the temperature of the glass substrate is 752°F (400°C) or more. This allows coating during substrate formation.
  • the glass substrate is moving at the time the iron doped tin oxide coating is deposited. This allows coating on a ribbon of glass in the float process.
  • the mixture is reacted over the glass substrate at essentially atmospheric pressure. This eliminates a need for costly vacuum apparatus.
  • the organic iron-containing compound is ferrocene or a derivative thereof.
  • the iron doped tin oxide coating is the outermost layer of the coated glass article.
  • the glass substrate is a soda-lime-silica glass. This reduces material cost.
  • the iron doped tin oxide coating is formed over a previously deposited sodium diffusion barrier layer.
  • the layer prevents sodium reaching the tin oxide coating.
  • the sodium diffusion barrier layer is comprised of silica.
  • the process further comprises feeding the gaseous mixture through a coating apparatus and discharging the gaseous mixture from the coating apparatus, wherein the coating apparatus is provided at a predetermined distance above and extends transversely across the glass substrate.
  • the tin-containing compound is a halogenated tin-containing compound.
  • the tin-containing compound is dimethyltin dichloride.
  • the oxygen is in the form of molecular oxygen.
  • the iron doped tin oxide coating exhibits a resistivity of at least 4 X 10 "2 ohm-cm.
  • the iron doped tin oxide coating exhibits a resistivity of at least 8 X 10 ohm-cm.
  • the glass substrate comprises a glass ribbon in a float glass
  • the gaseous mixture is delivered to a coating apparatus provided at a predetermined distance above and extending transversely across the glass ribbon, the glass ribbon being surrounded by float bath atmosphere, and the gaseous mixture is discharged from the coating apparatus and the gaseous mixture is directed toward and along the glass ribbon, the mixture reacting over the glass ribbon to form the iron doped tin oxide coating thereon.
  • a coated glass article comprising the features set out in claim 17.
  • the coated glass article comprises a glass substrate and an iron doped tin oxide coating, wherein the coating exhibits a resistivity of at least 4 X 10 "2 ohm-cm.
  • iron when added as a dopant in a tin oxide coating does not function as a conventional dopant to increase conductivity.
  • iron added to an otherwise undoped tin oxide coating simultaneously leads to higher sheet resistance and a decrease deposition rate, leading to a thinner coating and an increase in visible light transmission.
  • Fig. 1 depicts a schematic view, in cross-section, of a coated glass article in accordance with certain embodiments of the invention
  • Fig. 2 depicts a schematic view, in vertical section, of an installation for practising the float glass process in accordance with certain embodiments of the invention.
  • a CVD process for depositing an iron doped tin oxide coating (hereinafter also referred to as the "CVD process") is provided.
  • the CVD process will be described in connection with forming a coated glass article.
  • the coated glass article will be described for use in the manufacture of solar cells. It would be understood by one of ordinary skill in the art that the coated glass article could be utilized as a superstrate or substrate in the manufacture of solar cells.
  • the coated glass article described herein is not limited to solar cell applications.
  • the coated glass article may be utilized in architectural glazings, electronics, and/or have automotive and aerospace applications.
  • the iron doped tin oxide coating may be designated herein by the chemical formula Sn0 2 :Fe or abbreviated herein as TOFe.
  • the iron doped tin oxide coating contains primarily tin, oxygen and iron.
  • the iron doped tin oxide coating may also contain trace contaminants of, for example, carbon.
  • an iron doped tin oxide coating which is slightly oxygen deficient may also be deposited by the CVD process and may be useful.
  • the CVD process comprises providing a substrate.
  • the substrate is preferably glass.
  • the glass substrate has a deposition surface over which the iron doped tin 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 the CVD process.
  • a soda-lime-silica glass substrate may be a borosilicate glass.
  • 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 clear or a colored glass substrate and is not limited to a particular glass substrate thickness.
  • the glass substrate is heated when the iron doped tin oxide coating is deposited thereover.
  • the temperature of the glass substrate is 752°F (400°C) or more.
  • the temperature of the glass substrate is about 1 100°F (593°C) or more.
  • the temperature of the glass substrate is between about 1 100°F (593°C) and 1400°F (760°C) when the iron doped tin oxide coating is deposited thereover.
  • 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 the FIGURE.
  • 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 iron doped tin oxide coating.
  • the glass substrate moves at a predetermined rate of, for example, 3.175 m/min (125 in/min) or more as the iron doped tin oxide coating is being formed thereover.
  • 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 iron doped tin oxide coating is being formed.
  • the iron doped tin 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 iron doped tin oxide coating may be formed under low-pressure conditions.
  • the CVD process may comprise providing a source of a tin-containing compound, a source of water, a source of oxygen, and a source of an iron-containing compound.
  • these sources are provided at a location outside the float bath chamber.
  • reactant compound and “precursor compound” may be used interchangeably to refer to any or all of the tin-containing compound, water, oxygen, and iron-containing compound and/or used to describe the various embodiments thereof disclosed herein.
  • the CVD process also comprises forming a gaseous mixture of the precursor compounds.
  • 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 vapourized for use in the gaseous mixture.
  • the gaseous mixture includes precursor compounds suitable for forming the iron doped tin oxide coating at essentially atmospheric pressure. Once in a gaseous state the precursor compounds can be included in a gaseous stream and utilized to form the iron doped tin oxide coating.
  • the optimum concentrations and flow rates for achieving a particular deposition rate and iron doped tin oxide coating thickness may vary.
  • the gaseous mixture may comprise the tin-containing compound, water, oxygen, and iron-containing compound.
  • the tin-containing compound is a halogenated compound.
  • Preferable halogenated compounds include CI- containing compounds.
  • Preferred Cl- containing compounds for use as the tin-containing compound are dimethyltin dichloride (DMT), tin tetrachloride (SnCI 4 ) and monobutyltin trichloride (MBTC).
  • DMT dimethyltin dichloride
  • SnCI 4 tin tetrachloride
  • MBTC monobutyltin trichloride
  • Other tin-containing compounds are also suitable for use in the gaseous mixture.
  • the gaseous mixture may comprise water (H 2 0) in the form of water vapour or steam.
  • concentration of water vapour in the gaseous mixture may vary to achieve a desired growth rate. However, it has been discovered that with the addition of high concentrations of water vapour higher coating deposition rates are achieved.
  • Oxygen may be provided in the gaseous mixture as a part of a gaseous composition such as air. More preferably, oxygen is provided in a substantially purified form. In either embodiment, the oxygen is in the form of molecular oxygen.
  • the iron-containing compound is an organoiron compound.
  • the organoiron compound is ferrocene (Cp 2 Fe) or a derivative such as halogenated Cp 2 Fe.
  • other iron-containing compounds are suitable for use in the gaseous mixture.
  • the precursor compounds can be mixed without undergoing ignition and premature reaction.
  • the CVD process comprises mixing the precursor compounds to form the gaseous mixture.
  • the CVD process comprises mixing the tin-containing compound, water, oxygen, and iron-containing compound to form the gaseous mixture.
  • 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 fed through a coating apparatus and discharged from the coating apparatus utilizing one or more gas distributor beams prior to forming the iron doped tin oxide coating.
  • 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 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, 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 gaseous mixture be kept at a temperature below the thermal decomposition temperature of the precursor compounds to prevent pre-reaction and formation of the iron doped tin oxide coating before the mixture reaches the deposition surface of the glass substrate.
  • the gaseous mixture is maintained at a temperature below that at which it reacts to form the iron doped tin oxide coating and is delivered to a location near the deposition surface of the glass substrate, the glass substrate being at a temperature above the reaction temperature.
  • the gaseous mixture reacts at or near the deposition surface to form the iron doped tin oxide coating thereover.
  • the CVD process results in the deposition of a high quality coating on the glass substrate.
  • the iron doped tin oxide coating formed using the CVD process exhibits excellent coating thickness uniformity.
  • An additional feature of the CVD process is that it allows for the formation of iron doped tin oxide coatings at commercial viable deposition rates under dynamic deposition conditions.
  • the iron doped tin oxide coating is a pyrolytic coating.
  • the iron doped tin oxide coating exhibits a sheet resistance and a resistivity which is higher than an undoped tin oxide (Sn0 2 ) coating.
  • the glass article having the iron doped tin oxide coating formed thereover may exhibit a higher total visible light transmittance than a glass article having only an undoped tin oxide (Sn0 2 ) coating formed thereover.
  • total visible light transmittance refers to the percentage of visible light which passes through the glass article as measured from the side of the glass article where the deposition surface of the glass substrate is located.
  • the iron doped tin oxide coating is formed directly on the glass substrate.
  • the coated glass article resulting from utilizing the CVD process may be of a glass/TOFe arrangement.
  • the CVD process described herein may be utilized in combination with one or more additional coating layers to achieve a desired coating stack.
  • the additional coating layer(s) may be formed before or after forming the iron doped tin oxide coating.
  • the additional coating layer(s) may be formed in conjunction of the float glass manufacturing process or as part of another manufacturing process.
  • the additional coating layer(s) may be formed by pyrolysis or by another coating deposition process, and/or by utilizing one or more additional coating apparatuses.
  • the iron doped tin oxide coating may be formed directly on a tin oxide coating.
  • the tin oxide coating has been previously deposited over the deposition surface of the glass substrate.
  • the tin oxide coating comprises a dopant material such as, for example, fluorine.
  • a fluorine dopant is included in a tin oxide coating, the resistivity of the tin oxide coating is decreased.
  • the iron doped tin oxide coating may be formed directly on the fluorine doped tin oxide (Sn0 2 :F) coating at a thickness of 75 nanometers or less.
  • the fluorine doped tin oxide coating may be formed shortly before forming the iron doped tin oxide coating.
  • the fluorine doped tin oxide coating is formed in conjunction with the float glass manufacturing process.
  • the deposition of the fluorine doped tin oxide coating preferably takes place in the float bath section.
  • the fluorine doped tin oxide coating may be formed utilizing another manufacturing process.
  • the fluorine doped tin oxide coating may be formed by CVD, utilizing a coating apparatus and/or at essentially atmospheric pressure.
  • the fluorine doped tin oxide coating may be formed utilizing another deposition process, under low-pressure conditions, and without the use of a coating apparatus.
  • the iron doped tin oxide coating may be formed over a previously deposited sodium diffusion barrier layer or a color suppression interlayer.
  • Known sodium diffusion barriers such as, for example, a silica (Si0 2 ) coating are suitable for use with the CVD process.
  • known color suppression interlayers are suitable for use with the CVD process.
  • the iron doped tin oxide coating is formed as the outermost layer of the coated glass article.
  • additional coating layer(s) are formed after forming the iron doped tin oxide coating.
  • additional coating layer(s) of thin-film photovoltaic materials, or other semiconductor materials may be formed over the iron doped tin oxide coating so as to provide a desired coating stack.
  • the photovoltaic materials, or other semiconductor materials may be formed over the coated glass article during the manufacturing of solar cells.
  • 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 Fig. 2.
  • a float glass installation such as the installation 10 depicted in Fig. 2.
  • 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 preferred substrate over which the iron doped tin 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 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 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. On the molten tin surface, 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 the iron doped tin 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.
  • a coating apparatus 9 is shown within the float bath section 1 1 .
  • the coating apparatus 9 may be utilized in forming the iron doped tin oxide coating. However, depending on the thickness of the iron doped tin oxide coating desired and/or the need for additional coating layer(s), one or more additional coating apparatuses (not depicted) may be provided.
  • 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 1 1 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.
  • the iron doped tin oxide coating is preferably formed 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 1 1 and the annealing lehr 12 may be essentially atmospheric pressure.
  • Heat for maintaining the desired temperature regime in the float bath section 1 1 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 as by fans 26 in the cooling section 13.
  • Heaters 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
  • a laboratory furnace having a coating apparatus including a 10-inch wide bidirectional coater was provided.
  • the coating apparatus was utilized to direct gaseous precursor compounds to the deposition surface of a glass substrate in order to form a coating by chemical vapour deposition.
  • the precursor compounds Prior to forming the coating, the precursor compounds were vapourized and mixed to form a gaseous mixture.
  • the amounts of the individual gaseous precursor compounds in the gaseous mixtures of C1 , C1 A and Ex 1-Ex 4 are as listed in TABLE 1.
  • Each gaseous precursor mixture also comprised inert gases which made up the balance of the gaseous mixture. The total flow of each gaseous mixture is listed in TABLE 1 and expressed in standard liters per minute (slpm).
  • the glass substrates utilized in each of C1 , C1 A and Ex 1-Ex 4 were of a soda-lime- silica glass composition. Each glass substrate was heated to approximately 1 166°F prior to forming the coating. The coater, at the reactor face, or portion nearest the glass surface, was at a temperature of approximately 450°F. The line speed, i.e. the speed that the glass substrate moved beneath the coater portion of the coating apparatus, from which the gaseous precursor compounds were delivered, was 200 inches/minute. Thus, it should be appreciated that each glass substrate was moving at the time the coatings of C1 , C1A and Ex 1 -Ex 4 were deposited thereon.
  • examples C1 and C1A are illustrative of the same comparative deposition process. It should also be noted that the coated glass of C1 was formed prior to forming the coated glass articles of Ex 1-Ex 4. Additionally, it should be noted that the coated glass of C1 A was formed after forming the coated glass articles of Ex 1 -Ex 4. Thus, the results provided in TABLE 1 for examples C1 and C1A illustrate the repeatability of the comparative deposition process.
  • the coated glass articles of C1 and C1 A are each of a glass/Sn0 2 arrangement and the coated glass articles of Ex 1 -Ex 4 are each of a glass/Sn0 2 :Fe arrangement.
  • the coating thickness of the Sn02 coatings of C1 and C1 A are reported in TABLE 1.
  • the coating thickness of the Sn0 2 :Fe coatings of Ex 1-Ex 4 are also reported in TABLE 1.
  • the coating thicknesses were estimated by optical modelling using both the transmission spectra and reflection spectra of the coated glass articles of C1 and C1 A and of the coated glass articles of Ex 1-Ex 4.
  • the coating thickness of the Sn02 coatings of C1 and C1 A and the coating thickness of the Sn0 2 :Fe coatings of Ex 1-Ex 4 are reported in nanometers (nm).
  • the total visible light transmittance (% Tvis), sheet resistance (R s ), and resistivity (p) of the coated glass articles of C1 , C1A and Ex 1-Ex 4 are also reported in TABLE 1.
  • the total visible light transmittance is expressed as a percentage and was measured using a spectrophotometer.
  • the sheet resistance was measured using a four point probe and is expressed in ohm/sq, rounded down.
  • the resistivity was calculated by multiplying the sheet resistance by the coating thickness and is expressed in ohm-cm, rounded down to three decimal places.
  • the CVD process provides an improved process over the comparative deposition process illustrated by C1 and C1 A.
  • the sheet resistance of the coated glass article of Ex 1 was 3521.00 ohm/sq.
  • the sheet resistances for the coated glass articles of C1 and C1A were only 320.20 ohm/sq. and 564.60 ohm/sq., respectively. Additional improvements in sheet resistance are illustrated by Ex 2-Ex 4 where it was observed that as the percentage of iron-containing compound in the gaseous precursor mixture increased, the sheet resistance and resistivity of the resulting coated glass articles increased.
  • the iron doped tin oxide coating preferably exhibits a resistivity of at least 4 X 10 "2 ohm-cm, and more preferably a resistivity of at least 8 X 10 "2 ohm-cm.
  • the coated glass articles provided by Ex 1 -Ex 4 exhibited a higher total visible light transmittance than the coated glass articles of C1 and C1A. In fact, the coated glass articles provided by Ex 1-Ex 4 all exhibited a total visible light transmittance of 84% or more.
  • the CVD process described herein provides improvements over the comparative deposition process illustrated by C1 and C1A.
  • the inventors modelled examples and comparative examples at a constant coating thickness, so as to correct for the decrease in deposition rate. The inventors have found that iron added to an otherwise undoped tin oxide coating so as to achieve a constant coating thickness, nominally 300 nm. Results are shown in Table 2. TABLE 2
  • a coated article 1 according to the invention may comprise a glass substrate 2, a high refractive index layer 3, a low refractive index layer 4 and a high resistivity layer 5.
  • An example of a coated glass article according to the invention comprises a glass substrate provided with a coating stack formed of a layer of silicon on the glass, a layer of silica on the layer of silicon, and a layer of iron doped tin oxide on the silica, providing a visible light transmittance of about 20% and a film side reflectance of 70-75%.
  • the iron doped tin oxide coating exhibits a resistivity of at least 4 X 10 "2 ohm-cm, which may be suitable for discharging static electricity in certain applications where the coated glass article is used as a video display.
  • a coated glass article according to the invention may also be suitable as a mirror.

Abstract

La présente invention concerne un procédé CVD pour déposer un revêtement d'oxyde d'étain dopé au fer sur un substrat en verre, ainsi qu'un article en verre pourvu d'un revêtement d'oxyde d'étain dopé au fer. Le procédé consiste à préparer un mélange gazeux qui comprend un composé organique contenant de l'étain, de l'eau, de l'oxygène et un composé contenant du fer. Le mélange gazeux est dirigé vers et le long du substrat de verre, le mélange réagissant sur le substrat de verre pour y déposer le revêtement d'oxyde d'étain dopé au fer. L'article en verre est approprié pour un afficheur vidéo ayant une résistivité prédéterminée et une transmission élevée de la lumière visible.
PCT/GB2016/050401 2015-02-19 2016-02-17 Procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde d'étain dopé au fer, et article de verre revêtu ainsi obtenu WO2016132131A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562118223P 2015-02-19 2015-02-19
US62/118,223 2015-02-19

Publications (1)

Publication Number Publication Date
WO2016132131A1 true WO2016132131A1 (fr) 2016-08-25

Family

ID=55411702

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2016/050401 WO2016132131A1 (fr) 2015-02-19 2016-02-17 Procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde d'étain dopé au fer, et article de verre revêtu ainsi obtenu

Country Status (1)

Country Link
WO (1) WO2016132131A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US671767A (en) * 1900-11-28 1901-04-09 Max Moeller Berth for ships.
US6218018B1 (en) * 1998-08-21 2001-04-17 Atofina Chemicals, Inc. Solar control coated glass
WO2001072652A1 (fr) 2000-03-24 2001-10-04 Pilkington North America, Inc. Procede de formation de revetements d'oxyde d'etain dopes au niobium, et verre ainsi revetu
US6387514B1 (en) * 1998-03-20 2002-05-14 Glaverbel Solar control coated substrate with high reflectance
US6521295B1 (en) * 2001-04-17 2003-02-18 Pilkington North America, Inc. Chemical vapor deposition of antimony-doped metal oxide and the coated article made thereby
EP1624494A1 (fr) 2003-05-13 2006-02-08 Asahi Glass Company Ltd. Substrat conducteur transparent pour batterie solaire et procede de production dudit substrat
WO2015121632A1 (fr) 2014-02-11 2015-08-20 Pilkington Group Limited Article de verre revêtu et ensemble d'affichage fabriqué à partir de ce dernier

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US671767A (en) * 1900-11-28 1901-04-09 Max Moeller Berth for ships.
US6387514B1 (en) * 1998-03-20 2002-05-14 Glaverbel Solar control coated substrate with high reflectance
US6218018B1 (en) * 1998-08-21 2001-04-17 Atofina Chemicals, Inc. Solar control coated glass
WO2001072652A1 (fr) 2000-03-24 2001-10-04 Pilkington North America, Inc. Procede de formation de revetements d'oxyde d'etain dopes au niobium, et verre ainsi revetu
US6521295B1 (en) * 2001-04-17 2003-02-18 Pilkington North America, Inc. Chemical vapor deposition of antimony-doped metal oxide and the coated article made thereby
EP1624494A1 (fr) 2003-05-13 2006-02-08 Asahi Glass Company Ltd. Substrat conducteur transparent pour batterie solaire et procede de production dudit substrat
WO2015121632A1 (fr) 2014-02-11 2015-08-20 Pilkington Group Limited Article de verre revêtu et ensemble d'affichage fabriqué à partir de ce dernier

Similar Documents

Publication Publication Date Title
US10837108B2 (en) Chemical vapor deposition process for depositing a silica coating on a glass substrate
US8734903B2 (en) Process for forming a silica coating on a glass substrate
JP6039402B2 (ja) 酸化亜鉛被覆物品の作成方法
EP2825687B1 (fr) Procédé de dépôt chimique en phase vapeur permettant le dépôt de couches d'oxyde de zinc
US11542194B2 (en) Coated glass article, method of making the same, and photovoltaic cell made therewith
EP3417088B1 (fr) Procédé de dépôt chimique en phase vapeur pour le dépôt d'un revêtement
WO2016132131A1 (fr) Procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde d'étain dopé au fer, et article de verre revêtu ainsi obtenu
US20230202912A1 (en) Method of making a reflective coated glass article
EP3191423B1 (fr) Procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde de titane
US11485678B2 (en) Chemical vapor deposition process for forming a silicon oxide coating
WO2023247950A1 (fr) Articles en verre revêtus
WO2023227885A1 (fr) Procédé de formation d'un revêtement
WO2017137773A1 (fr) Procédé de dépôt chimique en phase vapeur pour déposer un revêtement d'oxyde métallique mixte et article revêtu ainsi formé

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16706243

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16706243

Country of ref document: EP

Kind code of ref document: A1