FR3133787A1 - MATERIAL COMPRISING A STACK WITH METAL ABSORBENT LAYER AND METHOD FOR DEPOSITING THIS MATERIAL - Google Patents

Abstract

The invention relates to a material comprising a substrate (10), glass, coated on one side (11) with a stack of thin layers (14) comprising at least one metallic functional layer (140) and at least two anti-reflective coatings (120). , 160), characterized in that said stack of thin layers (14) comprises, above said metallic functional layer (140) and opposite said substrate (10): - an overblocking layer based on oxide of titanium (152) located above and in contact with said functional metal layer (140) and having a thickness greater than or equal to 3.0 nm, and- an absorbent metal layer (168'), with a physical thickness of said absorbent metal layer (168') which is between 1.0 and 8.0 nm, said absorbent metal layer (168') being located directly on, or directly under, or indirectly under with the interposition of at least one layer comprising oxygen, an intermediate oxide dielectric layer (165). Abstract Figure: Figure 4

Description

MATERIAL COMPRISING A STACK WITH METAL ABSORBENT LAYER AND METHOD FOR DEPOSITING THIS MATERIAL

The invention relates to a material comprising a substrate coated on one face with a stack of thin layers with reflection properties in infrared and/or solar radiation comprising at least one, or even only one, metallic functional layer, in particular based on silver or a metal alloy containing silver and at least two anti-reflective coatings, said anti-reflective coatings each comprising at least one dielectric layer, said functional layer being arranged between the two anti-reflective coatings.

In this type of stack, the single, or each, metallic functional layer is thus arranged between two anti-reflective 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 an optical point of view, the aim of these coatings which surround the or each metallic functional layer is to “anti-reflect” this metallic functional layer.

It is known from international patent application No. WO 2010/142926 to apply radiation treatment after the deposition of a stack comprising a functional layer to reduce the emissivity or improve the optical properties of this stack, by providing in in particular an absorbent layer in the end layer of the stack. The use of an absorbent terminal layer makes it possible to increase the absorption of radiation by the stack and to reduce the power required for treatment. As the terminal layer oxidizes during treatment and becomes transparent, the optical characteristics of the stack after treatment are interesting (high light transmission can in particular be obtained).

This radiation treatment of the stack does not structurally modify the substrate.

It is also known from international patent application No. WO 2016/051069 to apply radiation treatment after the deposition of a stack comprising a metallic terminal layer consisting of zinc and tin, in Sn _x Zn _y with a ratio of 0.1 ≤ x/y ≤ 2.4 and having a physical thickness between 0.5 nm and 5.0 nm excluding these values.

It is further known from international patent application No. WO WO2016/193577 to apply radiation treatment after the deposition of a stack comprising on the one hand a terminal layer which is the layer of the stack which is the further from the face of the substrate, which comprises at least one metal M ₂ , said metal being a reducer in an oxide/metal couple having a redox potential γ ₂ and said terminal layer being in the metallic state and other leaves a pre-terminal layer which is the layer of the stack located just under and in contact with said terminal layer towards the face of the substrate, which comprises at least one metal M ₁ , said metal being a reducer in an oxide couple /metal having a redox potential γ ₁ and said pre-terminal layer being in the at least partially oxidized state, said redox potential γ ₁ being greater than said redox potential γ ₂ , said redox potentials being measured by a normal hydrogen electrode.

Radiation treatments are generally carried out by moving the substrate through an enclosure. It is desired that the substrate passes as quickly as possible because the productivity of the line increases with speed, but this speed must not be too high so that the treatment can actually produce the expected effect. In addition, too slow a speed can damage the stack of thin layers.

Furthermore, in the documents of the prior art, the essential absorbent layer is generally located in an end part of the stack, that is to say in a part as far away as possible from the surface of the carrier substrate. However, this part plays an essential role in the mechanical strength of the stack, and in particular the resistance to scratching, because it is through this part which is the first in contact with the scratching element. However, it is difficult to reconcile the two aspects; it is difficult to design a stacking end part which both integrates an absorbent layer intended to react during radiation treatment and at the same time presents high scratch resistance.

To improve the quality of the functional silver-based metal layers, it is known to use dielectric coatings under the silver layers comprising dielectric layers with a stabilizing function intended to promote wetting and nucleation of the silver layer. . Dielectric layers based on crystallized zinc oxide are used in particular for this purpose. In fact, the zinc oxide deposited by the sputtering process crystallizes without requiring additional heat treatment. The zinc oxide-based layer can therefore serve as an epitaxial growth layer for the silver layer.

Another way to prevent the degradation of the silver layers lies in the choice of the layer located above and in contact with the silver layer. Among the known proposals are the use of so-called blocking layers and/or dielectric layers based on crystallized zinc oxide. The objective is to protect the functional layers from possible degradation during deposition of the upper dielectric coating and/or during heat treatment.

The blocking layers are generally based on a metal chosen from nickel, chromium, titanium, niobium, or an alloy of these different metals. The different metals or alloys mentioned can also be partially oxidized, in particular having a sub-stoichiometry in oxygen (for example TiOx or NiCrOx).

These blocking layers are very thin, normally less than 2.0 nm thick and are susceptible at these thicknesses to being partially oxidized during heat treatment or during the deposition of an overlying layer. Generally speaking, these blocking layers are sacrificial layers, capable of capturing oxygen coming from the atmosphere or the substrate, thus preventing the oxidation of the silver layer.

Materials comprising, above the functional layer(s) based on silver, a sequence of a blocking layer based on a nickel and chromium alloy and a layer based on zinc oxide are currently used.

However, the use of these thin blocking layers, even associated with stabilizing layers based on zinc oxide, does not make it possible to obtain sufficiently high-performance glazing, notably having sufficiently low emissivity and good mechanical resistance. Indeed, it remains essential according to the invention that the advantageous emissivity properties are obtained without harming the mechanical resistance. Good mechanical resistance translates into good resistance to scratches and brushes, particularly in the EBT test (“Erichsen brush test”).

The invention is based on the discovery of a particular configuration of at least three layers in a stacking part terminating the stack, opposite the substrate (that is to say above the single metallic functional layer or above the metallic functional layer furthest from the substrate), or even four layers, or even more, in this stacking part; this configuration makes it possible to reduce the light absorption at the same speed of treatment by radiation of the stack according to known techniques, or to increase the speed of treatment by radiation of the stack according to known techniques while retaining the light absorption after low treatment.

The invention is further based on the discovery of a particular configuration terminating the stack which makes it possible both to integrate an absorbent layer and at the same time to obtain a stack having high mechanical resistance.

An aim of the invention is thus to succeed in developing a new type of stack of layers with one or more functional layers, a stack which presents, after treatment of the stack with radiation, high mechanical durability and transmission. high light.

In the particular configuration according to the invention, it is proposed to finish the stack, opposite the face of the substrate which carries it, with at least three layers:
- an overblocking layer based on titanium oxide, TiOx, located above and in contact with a single functional metal layer or a last functional metal layer of the stack and having a thickness greater than or equal to 3 .0 nm, in particular between 3.0 and 30.0 nm, or even between 5.0 and 30.0 nm,
- a metallic, absorbent layer with a physical thickness of 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, and
- an intermediate oxide dielectric layer, with the absorbent metal layer located:
* directly on (with contact) said intermediate oxide layer, or
* directly under (with contact) said intermediate oxide layer, or
* indirectly under said intermediate oxide layer with the interposition of at least one layer comprising oxygen.

Thus, this intermediate oxide layer can both:
- constitute an oxygen reservoir to allow the oxidation of the metal layer during treatment,
- itself constitute a layer of mechanical protection or have a nature compatible with the presence of an additional layer of mechanical protection, and
- contribute to obtaining high light transmission, as well as obtaining homogeneity of appearance, both in transmission and reflection.

Indeed, the applicant has discovered that good results in terms of resistance per square are obtained with a material comprising above the functional metal layer(s), in particular based on silver, a thick layer based on oxide of titanium in contact with silver. This layer is preferably deposited from a sub-stoichiometric ceramic target by controlling the oxygen in the deposition atmosphere. The functional metal layer/TiOx sequence makes it possible to reduce the emissivity. In addition, the presence of this high refractive index layer in contact with the functional metal layer contributes:
- to further improve the solar factor in the case where the stack is used as a low emissive stack on face 3 in double glazing, or
- to improve selectivity in the case where the stack is used as a solar control stack on face 2 in double glazing.

When using this functional metal layer/TiOx sequence, it is essential to properly control oxidation during sputtering of the titanium oxide layer. If we want to minimize absorption in the titanium oxide-based layer, a significant proportion of oxygen in the deposition atmosphere is required. However, if excess oxygen is introduced during sputtering of the first few nanometers of the titanium oxide layer, it causes oxidation of the functional metal layer. The resistivity of the functional metal layer is then degraded.

Finally, in the absence of oxygen or in the presence of a small quantity of oxygen during the spraying of the titanium oxide layer, a gain in resistance per square is observed. However, higher absorption and degraded mechanical properties are also observed. This results in poor EBT test scores.

The subject of the invention is therefore, in its broadest sense, a material comprising a substrate, glass, coated on one side with a stack of thin layers with reflection properties in infrared and/or solar radiation comprising at least one, or even just one, metallic functional layer, in particular based on silver or a metallic alloy containing silver and at least two anti-reflective coatings, said anti-reflective coatings each comprising at least one dielectric layer, said functional layer being arranged between the two anti-reflective coatings, said material being remarkable in that said stack of thin layers comprises, above said metallic functional layer and opposite said substrate:
- an overblocking layer based on titanium oxide located above and in contact with said functional metal layer and having a thickness greater than or equal to 3.0 nm, in particular between 3.0 and 30.0 nm, or even between 5.0 and 30.0 nm, and
- an absorbent metal layer, with a physical thickness of said absorbent 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, said absorbent metal layer being located directly on, or directly under, or indirectly under with the interposition of at least one layer comprising oxygen, an intermediate oxide dielectric layer.

Said absorbent metal layer preferably comprises at least one element chosen from Sn, Zn, Zr, Ti, In, Nb, Bi; it can consist of Sn, or Zn or Zr or Ti, or In, or Nb, or Bi or a mixture of Sn and Zn, or a mixture of Sn and In.

Said intermediate oxide dielectric layer preferably has a physical thickness which is preferably between 1.5 and 40.0 nm, or even between 2.6 and 30.0 nm, or even between 3.6 and 20.0. nm. Said intermediate oxide layer preferably comprises at least one element chosen from Sn, Zn, Zr. Said intermediate oxide dielectric layer is preferably a zinc tin oxide, which has high mechanical strength properties. Said intermediate oxide dielectric layer can itself be a final mechanical protection layer or be topped with a final mechanical protection layer.

In a variant, said absorbent metal layer is thus located below and in contact with a terminal protective layer, said terminal protective layer preferably being based on the oxide of one or more elements chosen from titanium, zirconium , silicon, zinc and tin and preferably having a thickness between 2.0 and 15.0 nm.

Said overlying anti-reflective coating may thus comprise a terminal protective layer, said terminal protective layer preferably being an oxide based on zinc and tin, which has high mechanical resistance properties. It can also be an oxide based on titanium oxide and in particular based on TiO _x or TiZrO _x .

An oxide dielectric overlayer may be interposed between said absorbent metal layer and said intermediate oxide dielectric layer, preferably above said absorbent metal layer, said oxide dielectric overlayer preferably having a physical thickness which is between 1.5 and 40.0 nm, or even between 2.6 and 20.0 nm, or even between 3.6 and 10.0 nm.

Said oxide dielectric overlayer preferably comprises at least one element chosen from Sn, Zn, Ti, Si, Zr.

Preferably, said oxide dielectric overlayer does not contain nitrogen in order to maximize the oxidation effect on the absorbent metal layer during treatment.

In a variant that is easier to manufacture, said oxide 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, in said absorbent metal layer. It can be, for example, TiO ₂ , ZrO ₂ , SiO ₂ , SnO ₂ , ZnO.

In another variant that is easier to manufacture, said oxide dielectric overlayer consists of an oxide having a composition which is over-stoichiometric in oxygen compared to the stable stoichiometry of the metallic element present, or metallic elements present s There are several of them in said absorbent metal layer. They can be for example TiO _x , ZrO _x , SiO _x , SnO ₂ , with x > 2.

Preferably, said dielectric overlayer does not consist of an oxide having a composition which is sub-stoichiometric in oxygen relative to the stable stoichiometry of the metallic element present, or of the metallic elements present if there are several, in said absorbent metal layer.

Said overlying anti-reflective coating preferably comprises a nitride dielectric layer, preferably a silicon-based nitride dielectric layer, said nitride dielectric layer preferably being spaced apart from said absorbent metal layer (i.e. i.e. with the interposition of at least one oxide dielectric layer between said nitride dielectric layer and said absorbent metal layer). This nitride dielectric layer includes nitrogen and, preferably, does not contain oxygen. Said nitride dielectric layer is preferably located on and in contact with said intermediate oxide dielectric layer.

Said metallic functional layer, or each metallic functional layer, 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 9.5 and 12.4 nm. , or even between 10.6 and 14.4 nm. The range of 7.2 and 9.5 nm, or even 7.2 and 8.5 nm, may be particularly suitable for stacking with a single metal functional layer and high light transmission.

Said overblocking layer based on titanium oxide can be obtained:
- by cathode sputtering,
- from a metallic titanium target or a ceramic target based on titanium oxide, preferably under stoichiometry.

When said overblocking layer based on titanium oxide is obtained from a metallic target, the deposition atmosphere includes significant proportions of oxygen.

Said overblocking layer based on titanium oxide located above and in contact with said functional metal layer is, preferably, deposited from a ceramic target, in particular sub-stoichiometric.

Said overblocking layer based on titanium oxide can be deposited from a ceramic target, in particular under stoichiometry preferably in an oxidizing atmosphere whose percentage in volume flow rate of oxygen represents between more than 0 and 20%, preferably 2 to 15%.

Said overblocking layer based on titanium oxide located above and in contact with said functional metal layer preferably comprises an oxidation gradient, a part of said overblocking layer based on titanium oxide further away of said functional metal layer being more oxidized than a part of said overblocking layer in contact with said functional metal layer. This part of said overblocking layer based on more oxidized titanium oxide can contribute to obtaining low light absorption.

In a variant, said absorbent metal layer is located above and in contact with said overblocking layer based on titanium oxide.

This thick overblocking layer based on titanium oxide, close to the metallic functional layer, contributes to obtaining the advantageous properties of the invention. This overblocking layer based on titanium oxide is non-absorbent, especially when it is mainly deposited from a ceramic target in an oxidizing atmosphere.

The overblocking layers based on titanium oxide comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 95.0%, at least 96.5% and better still at least 98 .0% by mass of titanium relative to the mass of all the elements constituting the overblocking layer based on titanium oxide other than oxygen.

The overblocking layers based on titanium oxide can have a thickness:
- greater than or equal to 3.0 nm, greater than or equal to 4.0 nm, greater than or equal to 5.0 nm, and/or
- less than or equal to 30.0 nm, less than or equal to 25.0 nm, less than or equal to 20.0 nm, less than or equal to 15.0 nm, less than or equal to 10.0 nm, less than or equal to 8.0 nm, less than or equal to 6.0 nm.

The overblocking layers based on titanium oxide may include elements other than titanium and oxygen. These elements can be chosen from silicon, chromium and zirconium. Preferably, the elements are chosen from zirconium. Preferably, the overblocking layer based on titanium oxide comprises at most 35%, at most 20% or at most 10% by mass of elements other than titanium relative to the mass of all the elements constituting the layer. overblocking based on titanium oxide other than oxygen.

According to a preferred embodiment, an overblocking layer based on titanium oxide can be deposited from a sub-stoichiometric TiO _x ceramic target, where x is a number different from the stoichiometry of the titanium oxide TiO ₂ , that is to say different from 2 and preferably less than 2, in particular between 0.75 times and 0.99 times the normal stoichiometry of the oxide. TiOx can in particular be such that 1.5 < x < 1.98 or 1.5 < x < 1.7, or even 1.7 < x < 1.95.

Said anti-reflective coatings located above said metallic functional layer may comprise two or more absorbent metallic layers.

Preferably, said anti-reflective coating located under said functional layer comprises, towards said substrate:
- a zinc-based oxide sub-layer, ZnO, which is located under and in contact with said functional layer, with a physical thickness of said zinc-based oxide sub-layer ZnO which is between 0.3 and 9.0 nm, or even between 1.0 and 7.0 nm, or even between 1.5 and 5.0 nm; And

- a titanium-based oxide dielectric sublayer, TiO₂, which is located under and in contact with said zinc-based oxide sub-layer ZnO, with a physical thickness of said titanium-based oxide sub-layer, TiO₂, 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.

In a specific variant, said antireflection coating located above said functional layer further comprises a dielectric sub-intermediate layer located between said metallic functional layer and said dielectric sub-layer, this dielectric sub-intermediate layer being preferably oxidized and comprising preferably a zinc oxide.

Said stack comprises a single metallic functional layer or may comprise two metallic functional layers, or three metallic functional layers, or four metallic functional layers; the metallic functional layers in question here are, preferably, continuous layers.

A metallic functional layer preferably comprises, in the majority, 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 made of silver.

By “metallic layer” within the meaning of the present invention, it must be understood that the layer does not contain oxygen or nitrogen.

By “absorbent layer” within the meaning of the present invention, it should be understood that 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 Ω.cm.

It is recalled that 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 which is identical for n and for k.

By “metallic absorbent layer” within the meaning of the present invention, it should be understood that the layer is absorbent as indicated above and that it does not contain any oxygen atoms or nitrogen atoms.

As usual, by “dielectric layer” within the meaning of the present invention, it must be understood that from the point of view of its nature, the layer is “non-metallic”, that is to say that it contains oxygen. or nitrogen, or both. In the context of the invention, 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 designates 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 which is identical for n and for k.

By “in contact” is meant within the meaning of the invention that no layer is interposed between the two layers considered.

By “based on” is meant in the sense of the invention that for the composition of this layer, the reactive elements oxygen, or nitrogen, or both if they are both present, are not considered and the element non-reactive (e.g. 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. This expression thus includes what is commonly referred to in the technique in question as "doping", whereas the doping element, or each doping element, can be present in quantities of up to 10 atomic%, but without the total dopant does not exceed 15 atomic% of non-reactive elements.

In a particular variant, said anti-reflective coating located under said functional layer does not include any layer in the metallic state. Indeed, it is not desired that such a layer could react at this location, and in particular oxidize, during treatment.

In a particular variant, said anti-reflective coating located under said functional layer does not include any absorbent layer. Indeed, it is not desired that such a layer could react at this location, and in particular oxidize, during treatment.

It is all the more surprising to achieve the properties targeted by the invention for these two previous variants because similar properties are sometimes obtained in the prior art with these two previous variants.

Preferably, said nitride dielectric layer does not contain zirconium.

Preferably, moreover, said nitride dielectric layer does not contain oxygen.

The present invention also relates to multiple glazing comprising a material according to the invention, and at least one other substrate, glass, 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 interposed gas blade is arranged between the two substrates.

Each substrate can be clear or colored. At least one of the substrates in particular may be mass-colored glass. The choice of the type of coloring will depend on the level of light transmission and/or the colorimetric appearance desired for the glazing once its manufacture is completed.

A substrate of the glazing, in particular the substrate carrying the stack, can be curved and/or tempered after deposition of the stack. It is preferable in a multiple glazing configuration that the stack is arranged so as to face the side of the interlayer gas blade.

The glazing can also be triple glazing made up of three sheets of glass separated two by two by a gas blade. In a triple glazing structure, the substrate carrying the stack can be on face 2 and/or on face 5, when we consider that the incident direction of the solar light passes through the faces in increasing order of their number .

The present invention also relates to a process for obtaining, or manufacturing, a material comprising a substrate, glass, coated on one face with a stack of thin layers with infrared reflection properties and/or in solar radiation comprising at least one, or even just one, metallic functional layer, in particular based on silver or a metallic alloy containing silver and two anti-reflective coatings, said anti-reflective coatings each comprising at least one dielectric layer, said functional layer being placed between the two anti-reflective coatings, said method comprising the following steps, in order:
- the deposition on one face of said substrate of a stack of thin layers with reflection properties in infrared and/or solar radiation comprising at least one, or even only one, metallic functional layer, in particular based on silver or metal alloy containing silver and at least two anti-reflective coatings, in order to form a material according to the invention, then
- the treatment of said stack of thin layers using a source producing radiation, in particular infrared radiation, and in particular laser radiation, in order to treat the stack of thin layers as such.

Said treatment is preferably carried out in an atmosphere not comprising oxygen and/or said treatment is carried out with the temperature of the face of the substrate opposite to the face treated by the radiation which does not exceed 100°C during said treatment, in particular does not exceed 50°C and even does not exceed 30°C.

According to the invention, it is possible to carry out rapid thermal annealing (“Rapid Thermal Process”) such as laser or flash lamp annealing. Rapid thermal annealing is for example described in applications WO2008/096089 and WO2015/185848. In these cases, only the stack is subjected to heat treatment. During this type of treatment, each point of the stack is brought to a temperature of at least 300 ^° C while maintaining a temperature less than or equal to 150 ^° C at any point on the face of the substrate opposite to that on which it is placed. locate the stack. This process has the advantage of only heating the stack, without significant heating of the entire substrate.

In the case of laser processing, the coated materials can be treated using a laser line formed from laser sources such as InGaAs laser diodes or Yb:YAG disk laser. These continuous sources emit at a wavelength between 900 and 1100 nm. The laser line has a length of around 3.3 m, equal to the width of the substrate, and an average width at half maximum FWHM between 45 and 100 µm.

The materials are arranged on a roller conveyor so as to move in a direction X, parallel to its length. The laser line is fixed and positioned above the coated surface of the substrate with its longitudinal direction Y extending perpendicular to the direction extending over this entire width.

The position of the focal plane of the laser line is adjusted to lie within the thickness of the functional coating when the substrate is positioned on the conveyor. The power density of the laser line at the focal plane is less than 100 kW/cm².

The speed of processing said stack of thin layers using a source producing radiation, in particular infrared radiation, and in particular laser radiation, is preferably between 8 and 20 m/min, or even between 10 and 20 m/min.

The details and advantageous characteristics of the invention emerge from the following non-limiting examples, illustrated using the attached figures:
- illustrates a first structure of a functional monolayer stack ending in an absorbent metal layer, the functional layer being deposited directly on a blocking underlayer and directly under a blocking overlayer, the stack being illustrated during the treatment with using a source producing radiation;
- illustrates a second structure of a functional single-layer stack ending in a terminal protective layer located on an absorbent metal layer;
- illustrates a third structure of a functional single-layer stack comprising an absorbent metal layer;
- illustrates a fourth structure of a functional single-layer stack comprising an absorbent metal layer;
- And each illustrate double glazing incorporating a stack according to the invention;
- illustrates the resistance per square, in ohms per square, of certain examples of stacks of thin layers as a function of the speed S of movement of the substrate in meters per minute during the treatment illustrated in And ;
- illustrates the light absorption LA, in percent, of certain examples of stacks of thin layers as a function of the speed S of movement of the substrate in meters per minute during the treatment illustrated in And ;
- illustrates the resistance per square, in ohms per square, of certain examples of stacks of thin layers as a function of the speed S of movement of the substrate in meters per minute during the treatment illustrated in And ; And
- illustrates the light absorption LA, in percent, of certain examples of stacks of thin layers as a function of the speed S of movement of the substrate in meters per minute during the treatment illustrated in And ;
In the has , the proportions between the thicknesses of the different layers or the different elements are not strictly respected in order to facilitate their reading.

THE has illustrate 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 a metal alloy containing silver, is placed between two anti-reflective coatings, the underlying anti-reflective coating 120 located below the functional layer 140 towards the substrate 10 and the overlying anti-reflective coating 160 placed above the functional layer 140 at the opposite the substrate 30. These two anti-reflective coatings 120, 160 each comprise at least one dielectric layer 122, 128; 164, 165, 166, 167, 169.

In , 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 over-blocking layer 152 located between the functional layer 140 and the anti-reflective coating 160.

Such a stack of thin layers can be used in multiple glazing 100 creating a separation between an exterior space ES and an interior space IS; this glazing can have a double glazing structure, as illustrated in Or : this glazing is then made up of two substrates 10, 30, which are held together by a frame structure 90 and which are separated from each other by an interposed gas blade 15.

In And , the incident direction of sunlight entering the building is illustrated by the double arrow on the left.

In , the stack 14 of thin layers is positioned on face 2 (on the outermost sheet of the building considering the incident direction of the solar light entering the building and on its face facing the gas blade), that is to say on an interior face 14 of the substrate 10 in contact with the interposed gas blade 15, the other face 11 of the substrate 10 being in contact with the exterior space ES. The substrate 30, not carrying a stack, has one face 29 in contact with the interposed gas blade 15, the other face 31 of the substrate 30 being in contact with the interior space IS.

In , the stack 14 of thin layers is positioned on face 3 (on the innermost sheet of the building considering the incident direction of the solar light entering the building and on its face facing the gas blade), that is to say on an interior face 11 of the substrate 10 in contact with the interposed gas blade 15, the other face 9 of the substrate 10 being in contact with the interior space IS. The substrate 30, not carrying a stack, has one face 29 in contact with the interposed gas blade 15, the other face 31 of the substrate 30 being in contact with the external space ES.

However, it can also be envisaged that in this double glazing structure, one of the substrates has a laminated structure.

A series of examples has been produced based on the stacking structure illustrated in with, starting from surface 14 of substrate 10, with a thickness of 4 mm, only the following layers, in this order:
- a dielectric layer of titanium dioxide, TiO ₂ 122 with a physical thickness of 24 nm, deposited from a titanium dioxide target in an atmosphere with 6.25% oxygen on the total oxygen and of argon and under a pressure of 2.10 ^-3 mbar;
- a zinc-based oxide layer, ZnO 128, with a physical thickness of 4 nm, deposited from a ZnO ceramic target, in an argon atmosphere and under a pressure of 2.10 ^-3 mbar;
- a metallic functional layer 140 based on silver, and more precisely here in silver, with a physical thickness of 13.5 nm, deposited from a metallic silver target, in an argon atmosphere and under a pressure of 8.10 ^-3 mbar;
- a sublocation layer based on titanium oxide, 152, having:
* a first part with a physical thickness of 5 nm, deposited from a TiO ₂ ceramic target, in an argon atmosphere and under a pressure of 2.10 ^-3 mbar;
* a second part of sublocation layer based on titanium oxide, 152' with a physical thickness of 5 nm, deposited from a ceramic target made of TiO ₂ , in an atmosphere of argon and oxygen, at 6.25% oxygen on the total oxygen and argon, and under a pressure of 2.10 ^-3 mbar;
- an intermediate dielectric layer of oxide 165 in mixed oxide of zinc and tin Sn _x Zn _y O, with a physical thickness of 15 nm, deposited from a metallic target containing 50% by weight of tin and 50% by weight of zinc in an atmosphere with 75% oxygen on the total argon and oxygen and under a pressure of 2.10 ^-3 mbar
- a nitride dielectric layer 166, based on silicon, here in Si ₃ N ₄ , with a physical thickness of 15 nm, deposited from a silicon target doped with aluminum, at 92% by weight of silicon and 8% by weight of aluminum in an atmosphere with 45% nitrogen on the total nitrogen and argon and under a pressure of 2.10 ^-3 mbar; And
- a dielectric layer of oxide 167, mixed zinc and tin Sn _x Zn _y O, with a physical thickness of 15 nm, deposited from a metallic target containing 50% by weight of tin and 50 % by weight of zinc in an atmosphere with 75% oxygen on the total argon and oxygen and under a pressure of 2.10 ^-3 mbar.

In this series, the stack described in the preceding paragraph constitutes a reference (“Ref.” in the figures).

In this reference structure, as well as in all the examples that follow:
- there is no sub-blocking layer 130 located between the underlying anti-reflective coating 120 and the functional layer 140;
- the second part 152' of the overblocking layer based on titanium oxide which is further away from the functional metal layer 140 and is more oxidized than the first part, in contact with the functional metal layer 140;
- each part of the overblocking layer based on titanium oxide is deposited from a sub-stoichiometric TiO _x ceramic target, where x is a number such as 1.7 < x < 1.95.

An example 1 ("Ex. 1" in the figures) was produced by placing on the substrate the same layers 122, 128, 140, 152, 152', 165, 166, 167, as for the reference, in the same order , with the same materials and the same thicknesses, then on layer 167 an absorbent metal layer 168, as visible in , in SnZn, with a physical thickness of 2 nm, deposited from a metallic target composed of 50% by weight of Sn and 50% by weight of Zn, in an argon atmosphere and under a pressure of 2.10 ^{- 3} mbar.

An example 2 ("Ex. 2" in the figures) was produced by placing on the substrate the same layers 122, 128, 140, 152, 152', 165, 166, 167, as for the reference, in the same order , with the same materials and the same thicknesses, then, as visible in , an absorbent metal layer 168, then a terminal protective layer 169:
- for this example 2, the absorbent metal layer 168 is made of SnZn, with a physical thickness of 2 nm, deposited from a metal target composed of 50% by weight of Sn and 50% by weight of Zn, in a argon atmosphere and under a pressure of 2.10 ^-3 mbar;
- the terminal protective layer 169 is made of titanium dioxide, TiO ₂ , with a physical thickness of 10.0 nm, deposited from a titanium dioxide target in an atmosphere with 6.25% oxygen on the total of oxygen and argon and under a pressure of 2.10 ^-3 mbar.

The elements Sn and Zn 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 Ω.cm.

Silver also has a ratio 0 < n/k < 5 over the entire visible wavelength range, but its electrical resistivity in the bulk state is less than 10 ^-5 Ω.cm.

There and the respectively illustrate on the ordinate the resistance per square, R, in ohms per square and the light absorption, LA, in percent, of the reference stacks, of Example 1 and of Example 2 after their deposition and after the treatment laser.

This laser treatment consisted here of moving the substrate 10 at a speed S varying from 7 meters per minute to 18 meters per minute under a laser line 20 with a continuous beam coming from a disk laser source Yb, YAG, d 'a wavelength of 1030 nm, 0.06 mm wide, 11.20 mm long and a total power density of 70 W/cm², with the laser line oriented almost perpendicular to face 11 (with a 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 has (the right black arrow illustrating the orientation of the emitted light), at a distance of 114 mm from face 11.

Before the laser treatment, the LA light absorption of the reference was 9% and that of Examples 1 and 2 was 22% and 24% respectively. The laser treatment caused the reduction in the light absorption LA and this reduction led to a final light absorption generally smaller for Example 1 and Example 2 than for the reference, at the same running speed, whatever the scrolling speed. It is therefore possible to increase the substrate travel speed, and thus increase productivity.

The speed of movement of the substrate during the treatment can be increased by approximately 2 meters per minute with the solution of example 1, the stack of which ends with the absorbent metal layer 168 compared to the reference and the speed can be increased approximately 5 meters per minute compared to the reference with the solution of example 2, the stack of which ends with the absorbent metal layer 168 then the terminal protective layer 169.

Scratch resistance was tested with a “Scratch Hardness Test 413” testing machine from the company ERICHSEN: a Van Laar hard metal tip with a diameter of 0.55 mm equipped with a tungsten carbide tip was moved and loaded. of a weight on the substrate at a given speed. We note the visibility through the area tested by the tip as a function of the load, in arbitrary units but comparable from one test to another. The mechanical resistance tests were carried out after deposition of the stack and after treatment of the stack with laser radiation, in an identical manner to the previous treatments.

Example 1 and example 2 always have a less visible scratch than the reference; this visibility is in particular close to zero for low loads. It is thus possible to benefit from the presence of the absorbent metal layer inside the overlying dielectric coating while maintaining high mechanical resistance.

Examples 1' and 2', identical respectively to Example 1 and Example 2, were produced by substituting the absorbent metal layer 168, made of SnZn, with a layer of titanium, deposited from a metal target. in bismuth in an argon atmosphere and under a pressure of 2.10 ^-3 mbar. Similar effects have been noted.

An example 3 ("Ex. 3" in the figures) was produced by placing on the substrate the same layers 122, 128, 140, 152, 152', 165, 166 and 167 as for the reference, in the same order, with the same materials and the same thicknesses, but also providing an absorbent metal layer 168', between the layer 152' and the layer 165, as visible in . For this example 3, this absorbent metal layer 168' is made of SnZn, with a physical thickness of 2 nm, deposited from a metal target composed of 50% by weight of Sn and 50% by weight of Zn, in a argon atmosphere and under a pressure of 2.10 ^-3 mbar.

An example 4 ("Ex. 4" in the figures) was produced by placing on the substrate the same layers 122, 128, 140, 152, 152', 165, 166 and 167 as for the reference, in the same order, with the same materials and the same thicknesses, but also providing, as visible in , an absorbent metal layer 168', then a dielectric overlayer 164 between, on the one hand, below, the layer 152' and on the other hand, above, the layer 165:
- for this example 4, the absorbent metal layer 168' is made of SnZn, with a physical thickness of 2 nm, deposited from a metal target composed of 50% by weight of Sn and 50% by weight of Zn, in an argon atmosphere and under a pressure of 2.10 ^-3 mbar; And
- the oxide dielectric overlayer 164 is made of titanium dioxide, TiO ₂ , with a physical thickness of 5.0 nm, deposited from a titanium dioxide target in an atmosphere with 6.25% oxygen on the total oxygen and argon and under a pressure of 2.10 ^-3 mbar.

There and the respectively illustrate on the ordinate the resistance per square, R, in ohms per square and the light absorption, LA, in percent, of the reference stacks, of Example 3 and of Example 4 after their deposition and after the same laser treatment as for examples 1 and 2.

Before laser treatment, the LA light absorption of Examples 3 and 4 was 22% and 27%, respectively. The laser treatment caused the reduction in the light absorption LA and this reduction led to a final light absorption generally smaller for Example 3 and Example 4 than for the reference, at the same running speed, whatever the scrolling speed. It is therefore possible to increase the substrate travel speed, and thus increase productivity.

The scratch resistance of Examples 3 and 4 is as good as that of Examples 1 and 2.

An example 5 and an example 6 were tested on the basis of example 4 by changing the oxide dielectric overlayer 164 in titanium dioxide, TiO ₂ , respectively by an oxide dielectric overlayer 164 in silicon dioxide, SiO ₂ , and oxide dielectric overlayer 164 in zinc oxide, ZnO. It was also found that the running speed of the substrate could be increased without the light absorption being too high (less than 8%).

Example 7 was tested on the basis of Example 4 by changing the oxide dielectric overlayer 164 in titanium dioxide, TiO ₂ , with a dielectric overlayer in silicon nitride, Si ₃ N ₄ . It was found that the light absorption was too high (between 12% and 16%) when the substrate running speed increased.

The present invention is described in the foregoing by way of example. It is understood that those skilled in the art are able to produce different variants of the invention without departing from the scope of the patent as defined by the claims.

Claims (14)

Material comprising a substrate (10), glass, coated on one face (11) with a stack of thin layers (14) with reflection properties in infrared and/or solar radiation comprising at least one, or even only one , metallic functional layer (140), in particular based on silver or a metal alloy containing silver and at least two anti-reflective coatings (120, 160), said anti-reflective coatings each comprising at least one dielectric layer (122, 165), said functional layer (140) being arranged between the two anti-reflective coatings (120, 160), characterized in that said stack of thin layers (14) comprises, above said metallic functional layer (140) and at the opposite said substrate (10):
- an overblocking layer based on titanium oxide (152) located above and in contact with said functional metal layer (140) and having a thickness greater than or equal to 3.0 nm, in particular between 3.0 and 30 .0 nm, or even between 5.0 and 30.0 nm, and
- an absorbent metal layer (168, 168'), with a physical thickness of said absorbent metal layer (168, 168') 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, said absorbent metal layer (168, 168') being located directly on, or directly under, or indirectly under with the interposition of at least one layer comprising oxygen, a layer intermediate oxide dielectric (165). Material according to claim 1, wherein said absorbent metal layer (168, 168') comprises at least one element chosen from Sn, Zn, Zr, Ti, In, Nb, Bi. Material according to claim 1 or 2, wherein said intermediate oxide dielectric layer (165) has a physical thickness which is between 1.5 and 40.0 nm, or even between 2.6 and 30.0 nm, or even between 3.6 and 20.0 nm and said intermediate oxide layer (165) preferably comprises at least one element chosen from Sn, Zn, Zr. Material according to any one of claims 1 to 3, wherein said absorbent metal layer (168) is located below and in contact with a terminal protective layer (169), said terminal protective layer (169) preferably being based oxide of one or more elements chosen from titanium, zirconium, silicon, zinc and tin and preferably having a thickness between 2.0 and 15.0 nm. Material according to any one of claims 1 to 3, in which an oxide dielectric overlayer (164) is interposed between said absorbent metal layer (168') and said intermediate oxide dielectric layer (165), said oxide dielectric overlayer (164) preferably having a physical thickness which is between 1.5 and 40.0 nm, or even between 2.6 and 20.0 nm, or even between 3.6 and 10.0 nm. Material according to claim 5, wherein said oxide dielectric overlayer (164) comprises at least one element chosen from Sn, Zn, Ti, Si, Zr. Material according to any one of claims 1 to 6, wherein said overlying anti-reflective coating (160) comprises a nitride dielectric layer (166), preferably a silicon-based nitride dielectric layer, said nitride dielectric layer (166 ) preferably being at a distance from said absorbent metal layer (168, 168'). Material according to any one of claims 1 to 7, in which said metallic functional layer (140) 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 14.4nm. Material according to any one of claims 1 to 8, wherein said overblocking layer based on titanium oxide (152) located above and in contact with said functional metal layer (140) is deposited from a ceramic target , particularly under stoichiometry. Material according to any one of claims 1 to 9, wherein said titanium oxide-based overblocking layer (152) located above and in contact with said functional metal layer (140) comprises an oxidation gradient, a portion of said overblocking layer based on titanium oxide further away from said functional metal layer (140) being more oxidized than a part of said overblocking layer in contact with said functional metal layer (140). Material according to any one of claims 1 to 3, 5 to 10, wherein said absorbent metal layer (168') is located above and in contact with said overblocking layer based on titanium oxide (152). Multiple glazing comprising a material according to any one of claims 1 to 11, and at least one other glass substrate (30), the substrates (10, 30) being held together by a frame structure (90), said glazing providing a separation between an exterior space (ES) and an interior space (IS), in which at least one spacer gas blade (15) is arranged between the two substrates. Method for obtaining a material comprising a substrate (10), glass, coated on one face (11) with a stack of thin layers (14) with reflection properties in infrared and/or solar radiation comprising at least one, or even just one, metallic functional layer (140), in particular based on silver or a metallic alloy containing silver and two anti-reflective coatings (120, 160), said anti-reflective coatings each comprising at least one dielectric layer (122, 164), said functional layer (140) being disposed between the two anti-reflective coatings (120, 160), said method comprising the following steps, in order:
- the deposition on one face (11) of said glass substrate (10), of a stack of thin layers (14) with reflection properties in infrared and/or solar radiation comprising at least one, or even only one, metallic functional layer (140), in particular based on silver or a metallic alloy containing silver and at least two anti-reflective coatings (120, 160), in order to form a material according to any one of claims 1 to 11, then
- the treatment of said stack of thin layers (14) using a source producing radiation and in particular infrared radiation. Method according to claim 13, in which said treatment is carried out in an atmosphere not comprising oxygen and/or said treatment is carried out with the temperature of the face of the substrate opposite to said face (11) treated by the radiation which does not does not exceed 100°C during said treatment, in particular does not exceed 50°C and even does not exceed 30°C.