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
  • C03C17/3644—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

Definitions

• the invention relates to a material and its deposition process, this material comprising a substrate coated on one face with a stack of thin layers with reflection properties in the infrared and/or in solar radiation comprising at least one metallic functional layer , in particular based on silver or on a metal alloy containing silver and at least two antireflection coatings, said antireflection coatings each comprising at least one dielectric layer, said functional layer being placed between the two antireflection coatings.
• the single, or each, metallic functional layer is thus disposed between two antireflection coatings each generally comprising several layers which are each made of a dielectric material of the nitride type, and in particular silicon nitride or aluminum, or oxide. From the optical point of view, the purpose of these coatings which frame the or each metallic functional layer is to "anti-reflect" this metallic functional layer.
• This radiation treatment of the stack does not structurally modify the substrate.
• the treatments are generally carried out by scrolling the substrate through an enclosure. It is desired that the substrate pass as quickly as possible because the productivity of the line increases with the speed but this speed must not be too high for the treatment to actually produce the desired effect. Also, too slow a speed can damage the stack of thin layers.
• the invention is based on the discovery of a particular configuration of two layers terminating the stack opposite the substrate which makes it possible to reduce the resistance per square measured after treatment at the same speed of treatment by radiation of the stack according to the techniques known, or to increase the rate of radiation treatment of the stack according to known techniques while maintaining the resistance per square measured after treatment.
• An object of the invention is thus to achieve the development of a new type of stack of layers with one or more functional layers, a stack which has, after rapid treatment of the stack by radiation, a low resistance per square ( and therefore low emissivity), high light transmission (and therefore low light absorption), as well as high mechanical durability.
• the material comprises a glass substrate, coated on one side with a stack of thin layers with reflection properties in the infrared and/or in solar radiation comprising at least one, or even just one, metallic functional layer, in particular base of silver or metal alloy containing silver and at least two antireflection coatings, said antireflection coatings each comprising at least one dielectric layer, said functional layer being placed between the two antireflection coatings, said material being remarkable in that , before the treatment of step b), said stack deposited in step a), opposite said substrate, ends starting from the substrate by:
• an absorbent metal layer with a physical thickness of said metal layer which is between 1.0 and 8.0 nm, or even between 1.5 and 5.0 nm, or even between 1.8 and 2.5 nm; then
• Said treatment of step b) is preferably carried out in an atmosphere not comprising oxygen.
• Said dielectric overlayer is thus located on and in contact with said absorbent metal layer and the stack does not include any other layer further from the surface of the substrate than said dielectric overlayer comprising oxygen.
• Said dielectric overlayer comprising oxygen preferably has a physical thickness which is between 5.6 and 25.0 nm, or even between 6.6 and 20.0 nm, or even between 7.6 and 15.0 nm, in order to increase mechanical durability.
• Said absorbent metal layer preferably comprises at least one element chosen from Sn, Zn, Ti, In, Nb; it may consist of Sn, or Zn or Ti, or In, or Nb or a mixture of Sn and Zn, or a mixture of Sn and In.
• Said dielectric overlayer preferably comprises at least one element chosen from Sn, Zn, Ti, Si, Zr.
• said dielectric overlayer is an oxide dielectric overlayer, or consisting of oxide of one or more elements, in order to maximize the oxidation effect on the absorbent metal layer during the treatment; as usual, "oxide” means that the layer (here the overlayer) does not contain nitrogen.
• this dielectric overlayer consists of an oxide having a composition which is the stable stoichiometry of the metallic element present or of the metallic elements present if there are several. It can be for example TiCh, ZrC, SiC, ZnO, SnC.
• this dielectric overlayer consists of an oxide having a composition which is over-stoichiometric in oxygen with respect to the stable stoichiometry of the metallic element present or of the metallic elements present if there are several. It can be for example TiOx, ZrO x , SiO x , SnO x , with x > 2.
• this dielectric overlayer does not consist of an oxide having a composition which is substoichiometric in oxygen with respect to the stable stoichiometry of the metallic element present or of the metallic elements present if there are several.
• said antireflection coating located under said metallic functional layer and/or said antireflection coating located above said metallic functional layer comprises a dielectric layer comprising nitrogen, preferably a dielectric layer of silicon-based nitride.
• said anti-reflective coating located under said functional layer comprises towards said substrate:
• a sub-layer of zinc-based oxide, ZnO which is located under and in contact with said functional layer, with a physical thickness of said sub-layer of zinc-based oxide ZnO which is between 0, 3 and 9.0 nm, even between 1.0 and 7.0 nm, even between 1.5 and 5.0 nm;
• TiOz a dielectric sub-layer of titanium-based oxide, TiOz, which is located under and in contact with said sub-layer of zinc-based oxide ZnO, with a physical thickness of said sub-layer of oxide at titanium base, TiOz, which is between 10.0 and 50.0 nm, or even between 15.0 and 45.0 nm, or even between 20.0 and 45.0 nm.
• said anti-reflective coating located above said functional comprises, opposite said substrate and under said absorbent metal layer:
• a layer of zinc-based oxide, ZnO with a physical thickness of said layer of zinc-based oxide ZnO which is between 2.0 and 10.0 nm, or even between 2.0 and 8.0 nm, or even between 2.5 and 5.4 nm;
• Said stack comprises a single metallic functional layer or may comprise two metallic functional layers, or three layers metallic functional layers, or four metallic functional layers; the metallic functional layers in question here are continuous layers.
• Said metallic functional layer, or each metallic functional preferably has a physical thickness which is between 7.2 and 22.0 nm, or even between 9.0 and 16.0 nm, or even between 10.6 and 14.4 nm , or even between 9.5 and 12.4 nm.
• the range of 7.2 and 9.5 nm, or even of 7.2 and 8.5 nm may be particularly appropriate for a stack with a single metallic functional layer and high light transmission.
• a metallic functional layer comprises, preferably, predominantly, at least 50% in atomic percentage, at least one of the metals chosen from the list: Ag, Au, Cu, Pt; one, several, or each, metallic functional layer is preferably silver.
• metal layer within the meaning of the present invention, it should be understood that the formulation of the composition of the layer does not contain oxygen or nitrogen.
• the layer is a material having an n/K ratio over the entire visible wavelength range (from 380 nm to 780 nm) between 0 and 5 excluding these values and having an electrical resistivity in the bulk state (as known in the literature) greater than 10' 5 ⁇ .cm.
• n designates the real refractive index of the material at a given wavelength and k represents the imaginary part of the refractive index at a given wavelength; the ratio n/k being calculated at a given wavelength identical for n and for k.
• metal absorbent layer within the meaning of the present invention, it should be understood that the layer is absorbent as indicated above and that the formulation of the composition does not contain any oxygen atom, nor any atom of nitrogen.
• dielectric layer within the meaning of the present invention, it should be understood that from the point of view of its nature, the layer is “non-metallic", that is to say that it comprises oxygen or nitrogen, or both.
• this term means that the material of this layer has an n/k ratio over the entire visible wavelength range (from 380 nm to 780 nm) equal to or greater than 5. It is recalled that n denotes the real refractive index of the material at a given wavelength and the coefficient k represents the imaginary part of the refractive index at a given wavelength, or absorption coefficient; the ratio n/k being calculated at a given wavelength identical for n and for k.
• in contact is meant in the sense of the invention that no layer is interposed between the two layers considered.
• the reactive elements oxygen, or nitrogen, or both if they are both present, are not considered and the non-reactive element (eg silicon or zinc) which is indicated as constituting the base, is present at more than 85 atomic % of the total non-reactive elements in the layer.
• the non-reactive element eg silicon or zinc
• This expression thus includes what is commonly referred to in the technique under consideration as “doping”, whereas the doping element, or each doping element, may be present in a quantity ranging up to 10 atomic %, but without the total dopant does not exceed 15 atomic % of the non-reactive elements.
• said antireflection coating located under said functional layer does not include any absorbent layer.
• said S13N4 silicon-based nitride dielectric layer does not include zirconium.
• said dielectric layer of nitride based on silicon SI-3N4 does not comprise oxygen.
• the present invention also relates to multiple glazing comprising a material according to the invention, and at least one other glass substrate, the substrates being held together by a frame structure, said glazing providing a separation between an exterior space and a interior space, in which at least one intermediate gas layer is arranged between the two substrates.
• Each substrate can be clear or colored.
• One of the substrates at least in particular can be made of glass colored in the mass. The choice of the type of coloring will depend on the level of light transmission and/or the colorimetric appearance sought for the glazing once its manufacture is complete.
• a substrate of the glazing in particular the carrier substrate of the stack, can be curved and/or tempered after the deposition of the stack. It is preferable in a multiple glazing configuration for the stack to be arranged so as to be turned towards the side of the spacer gas layer.
• the glazing may also be triple glazing consisting of three sheets of glass separated two by two by a gas layer.
• the carrier substrate of the stack can be on face 2 and/or face 5, when it is considered that the incident direction of the sunlight passes through the faces in increasing order of their number. .
• the present invention also relates to the material for implementing the process for obtaining, or manufacturing, according to the invention, that is to say the material of step a), before step b ) treatment.
• FIG. 1 illustrates a structure of a functional monolayer stack according to the invention, the functional layer being deposited directly on a blocking underlayer and directly under a blocking overlayer, the stack being illustrated during the treatment using a source producing radiation;
• FIG. 3 illustrates the resistance per square, in ohms per square, of some examples of stacks of thin layers as a function of the running speed S of the substrate in meters per minute during the treatment illustrated in FIG. 1;
• FIG. 4 illustrates the light absorption LA, in percent, of certain examples of stacks of thin layers as a function of the running speed S of the substrate in meters per minute during the treatment illustrated in FIG. 1;
• FIG. 5 illustrates the light absorption LA, in percent, of certain examples of stacks of thin layers as a function of the running speed S of the substrate in meters per minute during the treatment illustrated in FIG. 1 and as a function of the thickness of the last layer of the stack and the pressure inside the deposition chamber of this layer.
• FIG. 1 illustrates a structure of a functional single-layer stack 14 according to the invention deposited on a face 11 of a transparent glass substrate 10, in which the single functional layer 140, in particular based on silver or an alloy metal containing silver, is disposed between two antireflection coatings, the underlying antireflection coating 120 located below the functional layer 140 in the direction of the substrate 30 and the overlying antireflection coating 160 disposed above the functional layer 140 opposite the substrate 30.
• These two antireflection coatings 120, 160 each comprise at least one dielectric layer 122, 128; 162, 164, 166, 169.
• the functional layer 140 is located indirectly on the underlying anti-reflective coating 120 and indirectly under the overlying anti-reflective coating 160: there is an under-blocking layer 130 located between the underlying anti-reflective coating 120 and the functional layer 140 and an overblocking layer 150 located between the functional layer 140 and the antireflection coating 160.
• Such a stack of thin layers can be used in a multiple glazing 100 creating a separation between an exterior space ES and an interior space IS; this glazing may have a double glazing structure, such as illustrated in FIG. 2: this glazing then consists of two substrates 10, 30 which are held together by a frame structure 90 and which are separated from each other by an intermediate layer of gas 15.
• one of the substrates has a laminated structure.
• a first series of examples was produced on the basis of the stacking structure 14 illustrated in FIG. 1 with, starting from the surface 11 of the substrate 10, with a thickness of 4 mm, only the following layers, in this order:
• an overblocking layer 150 metallic, in titanium, with a physical thickness of 0.7 nm, deposited from a titanium target, in an argon atmosphere and under a pressure of 8 ⁇ 10 ⁇ 3 mbar;
• a silicon-based nitride dielectric layer SisN/i, 166 with a physical thickness of 25 nm, deposited from a silicon target doped with aluminum, 92% by weight silicon and 8% by weight aluminum in an atmosphere of 45% nitrogen on the total of nitrogen and argon and under a pressure of 2.10'3 mbar;
• a metallic layer 168 absorbent, in Sn x Zn y , with a physical thickness of 2 nm, deposited from a metallic target containing 50% by weight of tin and 50% by weight of zinc in an atmosphere of 'argon and under a pressure of 2.10' 3 mbar.
• the Sn and Zn elements each have a ratio 0 ⁇ n/k ⁇ 5 over the entire visible wavelength range and an electrical resistivity in the bulk state which is greater than 10' 5 ⁇ .cm.
• This laser treatment consisted here of a scrolling of the substrate 10 coated with the stack 14 on one side at a speed S varying from 7 meters per minute to 13 meters per minute under a laser line 20 with a continuous beam of a length wavelength of 973.1 nm, 0.06 mm wide, 11.20 mm long and total power of 453 W, with the laser line directed almost perpendicular to the face 11 (with an inclination of 7°) and in the direction of the stack 14, that is to say by arranging the laser line above the stack, as visible in FIG. 1 (the arrow straight black illustrating the orientation of the emitted light), at a distance of 114 mm from the face 11 .
• This curve shows that there is an interest in using a dielectric overlayer 169 of zirconium oxide, ZrCh, because the square resistance of the stack tends to be lower in the usual speed range, from 7 to 12 m. /minute.
• FIG. 4 illustrates the ordinate of the light absorption, LA, in percent, of the reference stack and of Example 1 thus deposited.
• LA the light absorption of the reference was 24.5% and that of Example 1 was 23.0%.
• the laser treatment caused the decrease in light absorption LA and this decrease is greater for example 1 than for the reference, whatever the scrolling speed. It is therefore possible to increase the running speed of the substrate, and thus increase productivity.
• a second series of three examples was produced on the basis of the structure of the reference stack with, in addition, a dielectric overlayer 169, in ZrC, which is located on and in contact with the metallic absorbing layer 168:
• the scratch resistance was tested with a "Scratch Hardness Test 413" test machine from the company ERICHSEN: a Van Laar hard metal tip with a diameter of 0.55 mm equipped with a tungsten carbide tip is moved and loaded with a weight on the substrate at a given speed. The visibility through the area tested by the tip is noted as a function of the load.
• examples 1 to 4 all show a less visible scratch than the reference and on the other hand that examples 1 and 2 show a scratch less visible than that of examples 3 and 4.
• Example 5 the same metal target, 50% by weight of tin and 50% by weight of zinc, was used for the two layers terminating the stack, but the dielectric overlayer 169 was deposited not in an atmosphere of pure argon as for the absorbent metal layer 168, but in an atmosphere of 14 argon and % oxygen.
• the dielectric overlayer 169 was deposited from a TiCh ceramic target, in an argon atmosphere containing approximately 6% oxygen.
• Example 8 which is a counter-example without an absorbent metal layer 168, the dielectric overlayer 169 was deposited in an atmosphere of 1 ⁇ 4 argon and % oxygen.
• the dielectric overlayer 169 was deposited from a silicon target with 92% by weight of silicon and 8% by weight of aluminum in an atmosphere of 45% nitrogen on the total of nitrogen and argon.
• the low speed value generates the low value of the square resistance range and the low value of the light absorption range
• the high speed value generates the high value of the square resistance range and the high value of the light absorption range
• the resistance per square increasing substantially constantly over the indicated range as a function of speed and the light absorption increasing substantially constantly over the entire indicated range as a function of speed.
• the treatment with the source producing the radiation does not produce a sufficient effect on the sheet resistance of the stack: the sheet resistance of 2.5 ohms per square is reached from a speed of 5 meters per minute, which is too slow.
• the light absorption remains much too high, whatever the speed, meaning that the oxidation effect on the absorbing metal layer 168 during the treatment at using the source producing the radiation is not achieved.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Surface Treatment Of Glass (AREA)

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• 2020
  • 2020-09-22 FR FR2009588A patent/FR3114264A1/fr active Pending
• 2021
  • 2021-09-21 EP EP21790948.0A patent/EP4217324A1/de active Pending
  • 2021-09-21 WO PCT/FR2021/051608 patent/WO2022064129A1/fr unknown

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