Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3652—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
  • C03C17/366—Low-emissivity or solar control 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
  • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
  • C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment

Definitions

• the insulated glazing unit preferably comprises a shading coefficient of less than or equal to 25%.
• the separation layer may preferably have a thickness of at least 0.5 nm; or preferably from 0.5 to 6 nm; more preferably from 0.5 to 5 nm.
• the separation layer preferably provides protection during the deposition process and during a subsequent heat treatment.
• the separation layer is preferably either essentially fully oxidised immediately after deposition, or it oxidizes to an essentially fully oxidized layer during deposition of a subsequent oxide layer.
• the separation layer may further comprise one or more chemical elements chosen from at least one of the following elements: Ti, V, Mn, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, Si, or from an alloy based on at least one of these materials, used for instance as dopants or alloyants.
• the base layer based on an (oxi) nitride of silicon and/or an (oxi)nitride of aluminium and/or alloys thereof of the lower anti-reflection layer comprises a thickness of from: 10 to 50 nm; 12 to 45 nm; or 15 to 40 nm.
• the base layer based on an (oxi)nitride of silicon and/or an (oxi)nitride of aluminium and/or alloys thereof of the lower anti -reflection layer comprises a thickness of from 15 to 30 nm. This base layer serves as a glass side diffusion barrier amongst other uses.
• (oxi)nitride of silicon encompasses both silicon (Si) nitride (SiN x ) and silicon (Si) oxinitride (SiO x N y ), whilst the term“(oxi)nitride of aluminium” encompasses both aluminium (Al) nitride (A1N X ) and aluminium (Al) oxinitride (A10 x N y ).
• the layer based on an oxide of zinc (Zn) and tin (Sn) and/or an oxide of tin (Sn) of the lower anti -reflection layer preferably serves to improve stability during a heat treatment by providing a dense and thermally stable layer and contributing to reduce the haze after a heat treatment.
• the layer based on an oxide of zinc (Zn) and tin (Sn) and/or an oxide of tin (Sn) of the lower anti -reflection layer may have a thickness of from 5 to 15 nm for a coated glass substrate with layer sequence comprising one silver-based functional layer.
• An upper thickness limit in the region of 15 nm is preferred due to optical interference conditions and by a reduction of heat treatability due to the resulting reduction in the thickness of the base layer that would be needed to maintain the optical interference boundary conditions for anti reflecting the functional layer.
• the layer based on an oxide of zinc (Zn) and tin (Sn) and/or an oxide of tin (Sn) of the lower anti -reflection layer preferably has a thickness of at least 12 nm. More preferably, the layer based on an oxide of zinc (Zn) and tin (Sn) and/or an oxide of tin (Sn) of the lower anti -reflection layer preferably has a thickness of from 12nm to 20nm.
• the layer based on an oxide of zinc (Zn) and tin (Sn) (abbreviation: ZnSnO x ) of the lower anti reflection layer may preferably comprise: 10 to 90 weight % zinc (Zn) and 90 to 10 weight % tin (Sn); more preferably about 40 to 60 weight % zinc (Zn) and about 40 to 60 weight % tin (Sn); even more preferably about 50 weight % each of zinc (Zn) and tin (Sn), in weight % of the total metal content of the layer.
• the layer sequence comprises two or more silver based functional layers
• that the lower anti -reflection layer comprises two or more layers of an (oxi)nitride of silicon and/or (oxi)nitride of aluminium and/or alloys thereof.
• Zinc oxide (ZnO) and mixed zinc (Zn) oxides have proven very effective as a growth promoting layer and thereby assisting in achieving a low sheet resistance at a given thickness of the subsequently deposited silver-based functional layer. It is preferred if the top layer based on an oxide of zinc (Zn) of the lower anti- reflection layer is reactively sputtered from a zinc (Zn) target in the presence of oxygen (O2), or if it is deposited by sputtering, a ceramic target, for example based on ZnO:Al, in an atmosphere containing zero or only a small amount, that is, generally no more than about 5 volume %, of oxygen.
• each silver-based functional layer is spaced apart from an adjacent silver-based functional layer by an intervening central anti -reflection layer.
• the intervening central anti- reflection layer(s) may comprise a combination of one or more of the following layers: a layer based on an (oxi)nitride of silicon and/or an (oxi)nitride of aluminium; a layer based on an oxide of Zn and Sn and/or an oxide of Sn; and a layer based on a metal oxide such as an oxide of Zn.
• each silver-based functional layer is spaced apart from an adjacent silver-based functional layer by an intervening central anti -reflection layer, wherein each central anti -reflection layer comprises at least, in sequence from the silver-based functional layer that is located nearest to the glass substrate, a layer based on an (oxi)nitride of silicon and/or an (oxi)nitride of aluminium; a layer based on an oxide of Zn and Sn and/or an oxide of Sn; and a layer based on a metal oxide such as an oxide of Zn.
• the coated glass pane according to the present invention preferably comprises also a barrier layer.
• the barrier layer is preferably located in direct contact with the silver based functional layer.
• the barrier layer may preferably be based on an oxide of Zn with a thickness of: at least 0.5nm, more preferably, the barrier layer is based on an oxide of Zn with a thickness of from 0.5 to 10 nm. Most preferably the barrier layer is based on an oxide of Zn with a thickness of from 1 to 10 nm.
• Further triple barrier arrangements may preferably be selected from the group consisting of the following combinations of layers in sequence from the silver-based functional layer: ZnO:Al/TiO x /ZnO:Al, ZnO:Al/ZnSnO x /ZnO:Al, TiO x /ZnSnO x /ZnO:Al, TiO x /ZnO:Al/TiO x , TiO x /ZnSnO x /TiO x , and ZnO:Al/ZnSnO x /TiO x .
• the barrier layer being based on an oxide of zinc (Zn)
• Zn oxide of zinc
• the barrier layer comprises a mixed metal oxide based on Nickel (Ni) and Chromium, such as a layer of sub stoichiometric NiCrO x .
• Ni Nickel
• Chromium such as a layer of sub stoichiometric NiCrO x .
• the layer of substoichiometric NiCrO x may also be used when the coated glass pane comprises a single silver-based functional layer.
• the barrier layer comprises a Nickel (Ni) and Chromium (Cr) metal alloy, that is a layer of NiCr, that it is possible to attain low internal and external reflections, especially if the NiCr metal alloy layer is used in direct contact over the first silver and is combined with an absorber in the lower ant-reflection layer.
• Ni Nickel
• Cr Chromium
• the coated glass preferably comprises an upper anti -reflection layer.
• the upper anti -reflection layer may preferably comprise:
• an uppermost barrier layer based on an oxide of nickel (Ni) and chromium or an oxide of zinc doped with aluminium (Al); and/or
• iii a layer based on an (oxi)nitride of silicon and/or an (oxi)nitride of aluminium; and/or iv) a layer based on an oxide of zinc (Zn) and tin (Sn).
• the layer based on an oxide of Zn and Sn and/or an oxide of Sn in the upper anti -reflection layer may preferably have a thickness of at least l .Onm; more preferably at least 3 nm or 4 nm, or even at least 5 nm, but preferably at least 6 nm; more preferably at least 7nm.
• the layer based on an oxide of Zn and Sn and/or an oxide of Sn in the upper anti -reflection layer preferably has a thickness of 12 nm or less; most preferably at most 10 nm; and especially from 5 to 9 nm.
• the layer based on an oxide of Zn in the upper anti -reflection layer may preferably have a thickness of at least 0.5 nm, more preferably at least 0.5 nm or 1 nm; or even at least 1.5 nm; but preferably less than 5 nm; more preferably 4 nm. These preferred thicknesses also enable further ease of deposition and improvement in optical characteristics such as haze whilst retaining mechanical durability.
• the layers in the upper anti -reflection layer are based on essentially stoichiometric metal oxides.
• barrier layers based on essentially stoichiometric metal oxides rather than metallic or less than 95% stoichiometric barrier layers leads to an extremely high optical stability of the coating during a heat treatment and effectively assists in keeping optical modifications during heat treatment small. Additionally, the use of layers based on essentially stoichiometric metal oxides provides benefits in terms of mechanical robustness.
• non-reactive sputtering includes sputtering an oxidic target in a low oxygen atmosphere (that is with zero, or up to 5 % volume oxygen) to provide an essentially stoichiometric oxide.
• a layer is said to be“based on” a particular material or materials, this means unless stated otherwise, the layer predominantly comprises said material or materials in an amount of at least 50 atomic %.
• ZnSnO x means a mixed oxide of Zn and Sn as described and defined elsewhere in the description.
• the layer in the upper anti -reflection layer based on an (oxi)nitride of aluminium or an (oxi)nitride of silicon may preferably comprise a thickness of at least 5 nm; preferably from 5 to 50 nm; more preferably from 10 to 45 nm; even more preferably from 10 to 40 nm; most preferably from 25 to 40 nm. Such thicknesses provide further improvement in terms of mechanical robustness of the coated pane.
• Said layer based on an (oxi)nitride of aluminium, an (oxi)nitride of silicon may preferably be in direct contact with the layer based on an oxide of zinc (Zn) in the upper anti -reflection layer.
• the layer based on an (oxi)nitride of aluminium, an (oxi)nitride of silicon may comprise a major part of the upper anti -reflection layer and provide stability (better protection during heat treatments) and diffusion barrier properties.
• Said layer is preferably deposited as an A1 nitride and/or Si nitride layer by reactive sputtering of a Si, A1 or mixed SiAl target, for example, of a S190AI 10 target in a N2 containing atmosphere.
• the composition of the layer based on an (oxi)nitride of aluminium and/or an (oxi)nitride of silicon may be essentially stoichiometric Si 9 oAlioN x .
• all individual layers of the upper and lower anti -reflection layers are preferably deposited with an essentially stoichiometric composition.
• the upper anti -reflection layers may comprise further partial layers consisting of suitable materials generally known for dielectric layers of low-e and/or solar control coatings, in particular chosen from one or more of the oxides of Sn, Ti, Zn, Nb, Ce, Hf, Ta, Zr, A1 and/or Si and/or of (oxi)nitrides of Si and/or A1 or combinations thereof.
• suitable materials generally known for dielectric layers of low-e and/or solar control coatings, in particular chosen from one or more of the oxides of Sn, Ti, Zn, Nb, Ce, Hf, Ta, Zr, A1 and/or Si and/or of (oxi)nitrides of Si and/or A1 or combinations thereof.
• any further layer may contain additives that modify its properties and/or facilitate its manufacture, for example, doping agents or reaction products of reactive sputtering gases.
• nitrogen may be added to the sputtering atmosphere leading to the formation of oxinitrides rather than oxides
• oxygen may be added to the sputtering atmosphere, also leading to the formation of oxinitrides rather than nitrides.
• the at least one absorbing layer may comprise a layer based on Ti, V, Cr, Fe, or W, Ni Nb, and alloys thereof and nitrides. More preferably the at least one absorbing layer is based on tungsten (W), preferably tungsten nitride or nichrome NiCr.
• the at least one absorbing layer based on tungsten is located in the lower anti-reflection layer and/or the upper anti -reflection layer.
• the at least one absorbing layer preferably contacts at least one layer based on an (oxi)nitride of Si and/or an (oxi)nitride of A1 and/or alloys thereof. More preferably the at least one absorbing layer is embedded between and contacts two layers based on an (oxi)nitride of Si and/or an (oxi)nitride of A1 and/or alloys thereof.
• This arrangement is beneficial in terms of exhibiting the lowest haze and having the potential to achieve the most neutral transmitted or reflected colours before and after heat treatment.
• the at least one absorbing layer contacts at least one layer based on a nitride of Al. More preferably the at least one absorbing layer is embedded between and contacts two layers based on a nitride of Al.
• the stack sequence for the coated glass substrate follows the sequence from the glass substrate:
• a preferred example of a stack sequence in relation to the present invention deposited in order from the glass substrate is preferably therefore:
• Experiment 1 Comparison of results for glass substrates coated with a layer sequence according to the present invention which includes at least one absorber layer.
• the coating layers were deposited on a 4mm thick standard float glass pane with a light transmittance in the region of 88% using single or dual magnetrons equipped with MF-AC and/or DC magnetron (or pulsed DC) power supplies.
• the functional layers of essentially pure silver (Ag) were sputtered from silver targets in an Ar sputter atmosphere without any added oxygen and at a partial pressure of residual oxygen below 10 "5 mbar.
• the layers of silicon nitride (SiN x ) were reactively sputtered from mixed Si 90 Al 10 targets in an Argon/Nitrogen (Ar/N2) sputter atmosphere containing only residual oxygen.
• NiCrNx nickel chromium nitride
• the layers of silicon oxide (SiOx) were sputtered from mixed SLoAho targets in an Argon/Oxygen (Ar/Ck).
• the layers of AIN were reactively sputtered from an A1 target in an Argon/Nitrogen (Ar/N2) sputter atmosphere containing only residual oxygen.
• the layers of ZAO were sputtered from a ceramic ZnO:Al target (with an aluminium (Al) content in the region of 10 weight %) in an Ar/02 sputtering atmosphere.
• NiCrOx The layers of NiCrOx were sputtered reactively from Nickel -Chromium alloy targets (with approximately 80 weight % nickel (Ni) and 20 weight % chromium (Cr)) in and Ar/0 2 sputtering atmosphere.
• the coating stack layers were deposited using standard process conditions.
• Table 1 results for silver based low emissivity coating stacks applied to float glass sheets in the presence of at least one absorber layer.
• Tables 1 and 2 provide details of the layer sequences for a comparative coated glass substrates and coated glass substrates according to the present invention.
• Tables 1 and 2 The methodology used to collect the data in Tables 1 and 2 is set out below. For each example, the layers were deposited on a glass pane in the sequence shown starting with the layer at the top of each column. Table 3 provides details of the light transmission measurements recorded for the coatings of Comparative Examples 1, 2 3 and Examples 4 to 11 after heat treatment.
• Table 3 illustrates the light transmission measurements recorded for the coatings of comparative Examples 1, 2 3 and Examples 4 to 11 after heat treatment
• Table 4 illustrates the colour measurements recorded according to the CIE colour system for the coatings of Comparative Examples 2 and 3 and Examples 4, 9, 10 and 11 when installed in an insulated glazing unit (IGU).
• IGU insulated glazing unit
• Rg a* and Rg b* represent the colour co-ordinates according to the CIE colour system for the uncoated side of the glass substrate.
• Rg Y represents the reflection for the uncoated side of the glass substrate.
• Rc Y represents the reflection for the coated side of the glass substrate.
• Shading Coefficient is a measure of the total amount of heat passing through the glass substrate (known as the total solar heat transmittance) compared with that through a single clear glass.
• the shading coefficient (SC) is derived by comparing the solar radiant heat transmission properties of any glass with a clear float glass having a total solar heat transmittance of 0.87 (that is, clear float glass about 4mm thick).
• coated glass substrates according to the present invention with a coating deposited by physical vapour deposition (PVD) (or sputtering) followed by heat treatment and toughening, which provide the required colour and solar control properties demanded by the glazing industry, and which are able to be incorporated into an insulated glazing unit and still retain the required colour and when viewed from either side of the glazing unit.
• PVD physical vapour deposition
• the inventors have found that it is possible to produce toughenable coated glass substrates in which the internal and external reflections are minimized by using one or more stable absorber in combination with dielectric layers in a set order from the glass substrate.
• the inventors have surprisingly found that by using one or more stable absorber layer in combination with a series of dielectric layers in a coating for a glass substrate that it is possible to prepare an insulated glazing unit (IGU) again with minimal internal and external reflection whilst appearing neutral or grey for the transmitted colour .
• IGU insulated glazing unit
• the inventors have therefore found that to achieve the required colour in transmission and also low internal and external reflections, it is most preferable to use a single absorber layer in the dielectric layer closest to the glass substrate and preferably also a second absorber layer in the stack design. Further, the inventors have found that it is preferable to position the second absorber layer above either the first and/or second silver based functional layer, and therefore in a middle or upper portion of the layer sequence, that is furthest from the glass substrate. The inventors have also found that low reflections may be achieved by using a NiCr metal alloy layer in contact with the first silver functional layer with a first absorber layer in the lower anti- reflection layer.
• the second absorber layer is preferably positioned after a barrier layer (such as for example NiCrOx) in the middle or upper portion of the layer sequence.
• a barrier layer such as for example NiCrOx
• the present invention demonstrates that it is possible to achieve optimised solar control properties in a PVD (or sputtered) deposited stack sequence using one or more absorber layers whilst retaining a grey or neutral colour in transmission for the coated glass substrate which when incorporated into an insulated glazing unit is able to achieve a shading coefficient of preferably 25% or less and a Selectivity (light transmission (LT) to Total Solar Heat Transmission (TSHT)) of preferably between 1.50 and 1.55.
• LT light transmission
• TSHT Total Solar Heat Transmission

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• Chemical & Material Sciences (AREA)
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• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Surface Treatment Of Glass (AREA)

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• 2019
  • 2019-08-01 GB GBGB1910980.0A patent/GB201910980D0/en not_active Ceased
• 2020
  • 2020-07-31 WO PCT/GB2020/051857 patent/WO2021019259A1/en active Application Filing
  • 2020-07-31 EP EP20751654.3A patent/EP4007744A1/de active Pending

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