WO2020058061A1 - Material having optical and aesthetic properties - Google Patents

Abstract

The invention relates to a material with neutral optical properties, having a chromatic neutralisation function when comprising stacks that contain metallic functional layers. The material comprises a transparent substrate having, on and in contact with at least one of its surfaces, a first layer based on zinc nitride and tin nitride and/or based on nickel nitride and chromium nitride.

Description

 Description

Title of the invention: Material with optical and aesthetic properties

 [0001] [The present invention relates to a material with neutral optical properties having a chromatic neutralization function when it comprises stacks containing metallic functional layers. The invention also relates to a method for obtaining such a material.

 The share of glass surfaces in buildings and vehicles continues to

 grow to meet users' need for natural light.

 For reasons of energy saving and comfort, the glass surfaces

 can be functionalized in order to act on incident solar and / or infrared radiation and reduce "greenhouse effect" phenomena. The functionalization of these surfaces is generally carried out by depositing on said surfaces a stack of layers comprising metallic functional layers. These layers give the surfaces, as well as the glazing units which comprise them, so-called "selective" functions making it possible to reduce the amount of energy transmitted through the glazing unit towards the interior.

 To these selective thermal functions can also be added

 aesthetic requirements in terms of color. In certain applications, in particular in the building, the glazed surfaces must present in

 transmission, in external and / or internal reflection, a surface appearance of neutral color, that is to say preferably close to the gray color in the blue-green chromatic range.

 [0005] However, the use of functional stacks making it possible to confer

selective thermal functions on glass surfaces is generally not very compatible or even antagonistic to aesthetic requirements in terms of color. In particular, the optical properties of these stacks of functional layers do not make it possible to easily obtain a neutral color. For example, in the most widespread case of stacks comprising metallic functional layers based on silver, it is necessary to make complex adjustments between the thicknesses of the functional layers, on the one hand, and the nature and the optical thickness of the layers constituting the dielectric assemblies which separate them, on the other hand. These adjustments condition the optical interactions between the different layers. It is then a question of finding a compromise between thermal and aesthetic properties.

 The problem is further complicated when there is a need to maintain a high light transmission or an inconspicuous shimmering effect. In particular, the thickening of metallic functional layers based on silver can no longer be used as a means of imparting a neutral color to the material in which they are included.

 A possible alternative is to color the bulk of the substrate constituting the glass surface by incorporating coloring additives in its composition. For example, in the case of mineral glass substrates, it is possible to use coloring oxides which are incorporated into the vitrifiable mixture used to manufacture them.

 One of the main drawbacks of this method is that it is necessary to develop dedicated processes or to modify existing processes for the exclusive production of such tinted substrates. For example, when tinted mineral glass substrates are produced on production lines based on the flotation process, these lines can only produce one shade at a time. It is then necessary to produce a certain amount of glass for each shade which will then be stored for several months or even years before being sold. It can result in a material and economic loss in the event of unsold goods or a lack of supply if the entire stock is sold.

Due to the costs generated by this method, a limited number of manufacturers can implement it. It may result that a customer or a processor becomes dependent on this limited number of suppliers, or even on a single supplier, as well as on a limited number of mineral glass substrate compositions which may not be adapted to new needs. . This situation of economic and material dependence can quickly be detrimental for the development of new products.

 The present invention solves these problems. It relates to a material comprising a transparent substrate which comprises on and in contact with at least one of its surfaces a first absorbent layer based on zinc nitride and tin and / or nickel nitride and chromium.

 The material of the invention has a neutral color, that is to say a

gray color in the blue-green chromatic range. In particular, the values of the two parameters a ^* and b ^* in the L ^* a ^* b ^{* system} are close to zero, in particular in transmission and in external reflection.

 The material of the invention also has a neutralization function

 chromatic when used as a support for a stack of thin layers containing metallic functional layers, in particular metallic thin layers based on silver. In other words, when the material serves as a support for a stack containing metallic functional thin layers, it makes it possible to neutralize the color of said stack and to keep a generally neutral color. It also makes it possible to reduce the physical thickness of the functional metallic thin layers and / or of the other metallic thin layers included in the stack without prejudice to the optical and thermal performance of the stack.

 Another advantage of the material of the invention is that it is easier to

 manufacture only those obtained by methods based on a coloring in the mass of the substrate or, if necessary, on an adjustment of the physico-chemical characteristics of the thin layers constituting the stacks for which it is capable of serving as a support. An example of a process for obtaining the material of the invention is described below.

The substrate included in the material of the invention is transparent. It is preferably undyed in the mass, although it can be so as long as this is not detrimental for its transparency. In this sense, the invention has the other advantage of being able to be produced with many types of transparent substrates. Several embodiments of the invention are described below, the characteristics of which are illustrated in the figures.

 [Fig. 1] is a schematic representation of a first embodiment of a material according to the invention.

 [Fig. 2] is a schematic representation of a second mode of

 production of a material according to the invention.

 [Fig. 3] is a schematic representation of a third mode of

 production of a material according to the invention.

 [Fig. 4] is a schematic representation of a cross section of double glazing comprising a material according to the invention.

 [Fig. 5] is a schematic representation of a cross section of a single glazing unit comprising a material of the invention.

 In the following text, it refers to the figures in which the numbers relate to the elements described below.

 In this description, it uses definitions and conventions

 following.

 The position of the substrate can be horizontal, vertical or inclined depending on the choice made for the implementation of the invention. The order in which the layers or sets of layers are listed is defined from the substrate in the direction of the surface of the stack opposite the substrate. For example, a metallic functional layer F1 and a dielectric set of layers E1 are the closest to the substrate. A metallic functional layer F3 and a dielectric set of layers E4 are the most distant from the substrate.

The term "above", respectively "below", qualifying the position of a layer or a set of layers and defined relative to the position of a functional layer, means that said layer or said set of layers is closer, respectively farther, from the substrate. These two terms, "above" and "below", do not mean that the layer or set of layers that they qualify and the functional layer with respect to which they are defined are in contact. They do not exclude the presence of others intermediate layers between these two layers. The expression "in contact" is explicitly used to indicate that no other layer is disposed between them.

 The term "exterior", respectively "interior", when it qualifies a

 surface of the substrate or an optical or physical parameter of a surface of the substrate, designates the surface of the substrate oriented towards the outside, respectively inside, of the room, for example a building or a vehicle, in which the substrate is used .

Without any precision or qualification, the term "thickness" used for a layer corresponds to the physical thickness, real or geometric, e, of said layer. It is expressed in nanometers. The expression "optical thickness" is used to indicate explicitly the optical thickness, denoted eo, of a layer. It is defined by the relation eo = n ^* e where n is the refractive index of the layer and e its physical thickness, real or geometric. The refractive index of the layers is measured at the electromagnetic wavelength of 550nm.

 The optical thickness is also expressed in nanometers.

 The expression “dielectric set of layers” designates one or more layers in contact with each other forming a generally dielectric stack, that is to say that it does not have the functions of a layer metallic functional. If the dielectric assembly comprises several layers, these may themselves be dielectric. The physical, real or geometric thickness, respectively the optical thickness, of a dielectric set of layers, corresponds to the sum of the physical, real or

 geometric, respectively optical thicknesses, of each of the layers which constitute it.

 In the present description, the expression "based on", used to qualify a material or a layer as to what it or it contains, means that the mass fraction of the constituent that he or she comprises is d at least 50%, in particular at least 70%, preferably at least 90%.

Light transmission, light reflection and the solar factor are defined, measured and calculated in accordance with standards EN 410, EN 613, ISO 9050 and ISO 10292. Color is measured in the L ^* a ^* b ^* CIE 1976 color space according to ISO 11664 with an illuminant D65 and a 2 ° field of view for the reference observer.

 The noun "stoichiometry" and its derived adjectives must be interpreted according to the conventional sense of the technical field. It means in particular that the proportions of the chemical elements constituting a compound correspond to those of the "defined compound" as defined by thermochemical diagrams or conventions in force in the technical field.

 A first embodiment of the material of the invention is shown schematically in Figure 1. The material 1000 comprises a transparent substrate 1001 and a first layer 1002 based on zinc nitride and tin and / or based nickel nitride and chromium. The first layer 1002 is on and in contact with at least one of the surfaces 1001a of the transparent substrate 1001.

 The physical thickness of the first 1002 based on zinc and tin nitride and / or based on nickel and chromium nitride can be between 2 and 20 nm. In a preferred embodiment, the physical thickness is at least 2 nm. The zinc and tin nitride and / or the nickel and chromium nitride of the first layer may or may not be stoichiometric.

 The first layer 1002 can be a layer based on zinc nitride and

 of tin. By way of nonlimiting example, the atomic ratio of zinc to tin, Zn: Sn, can be between 1 and 9. The atomic ratio of nitrogen N to the sum of zinc plus tin, N: (Zn + Sn) , can be between 0.1 and 1.5. In particular, the atomic ratio Zn: Sn may advantageously be between 1, 4 and 8, and the atomic ratio N: (Zn + Sn) may be between 0.5 and 1.

The real part of the refractive index at 550 nm of the first layer based on zinc nitride and tin is advantageously between 2.4 and 4. The optical thickness of the first layer based on zinc and tin nitride can vary between 4.5 nm and 80 nm. The first layer 1002 can be a layer based on nickel nitride and chromium. By way of nonlimiting example, the atomic ratio of zinc to tin, Ni: Cr, can be between 1 and 4. The atomic ratio of nitrogen N to the sum Ni plus Cr, N: (Ni + Cr) , can be between 0.3 and 1. In particular the atomic ratio Ni: Cr can advantageously be between 2 and 4, and the atomic ratio N: (Ni + Cr) can be between 0.5 and 1.

 In a variant of the first embodiment of the invention, the material

1000 consists of a transparent substrate 1001 and a first layer 1002 based on zinc and tin nitride and / or based on nickel and chromium nitride. The first layer 1002 is on and in contact with at least one of the surfaces

1001 has transparent substrate 1001.

In other embodiments of the material of the invention, the transparent substrate further comprises on and in contact with said first layer a stack of thin layers comprising at least one functional metallic layer.

 In a second mode of the material according to the invention, the stack of

 thin layers comprises two metallic functional layers separated by a dielectric set of thin layers. This embodiment is shown diagrammatically in FIG. 2. The material 2000 comprises a transparent substrate 1001 and a first layer 1002 based on zinc nitride and tin and / or based on nickel nitride and chromium, said first layer

1002 being on and in contact with at least one of the surfaces 1001 a of the transparent substrate 1001. A stack 2001 of thin layers comprising two functional metallic layers 2004, 2008 is placed on and in contact with the surface 1002a of said first layer 1002. The two layers

 functional metal 2004, 2008 are separated by a set

 2006 thin film dielectric.

In the embodiment shown in FIG. 2, the stack 2001 of thin layers also comprises a dielectric assembly 2002 between the first layer 1002 and the first metallic functional layer 2004, and a dielectric assembly 2010 of layers between the second metallic functional layer 2008 and the surface of the stack 2001 a. The stack 2001 can further comprise a so-called blocking layer 2005, 2009 placed above and in contact with a functional metallic layer 2004, 2008. The function of this layer, generally of very thin thickness, is to protect the metal layer when the deposition of the subsequent layer is carried out in an oxidizing atmosphere or when certain elements such as oxygen are liable to migrate from one layer to another during a heat treatment. If it is necessary to protect each

 functional metal 2004, 2008, it is advantageous that a blocking layer 2005, 2009 is placed above and in contact with each layer

 functional metal 2004, 2008 that includes the 2001 stack. This layer is preferably based on the metals or alloys chosen from Ti and NiCr. Its thickness is generally equal to or less than 5 nm.

 It is also possible to have a blocking layer 2003, 2007 below and in contact with a functional metallic layer 2004, 2008. If it is necessary to protect each functional metallic layer 2004, 2008, it may be advantageous that a blocking layer 2003, 2007 is placed below and in contact with each functional metallic layer 2004, 2008 which comprises the stack 2001.

 It may be advantageous for certain applications that the entire stack 2001 includes a protective layer 2011 in order to protect it from possible physicochemical alterations by the atmosphere or the external environment with which it is susceptible. to be in touch. In this sense, the stack 2001 of layers may further comprise a protective layer 2011 disposed above its surface capable of being in contact with the atmosphere. The physical thickness of said protective layer is generally equal to or less than 5 nm. By way of nonlimiting example, the protective layer may be a layer based on TiZr alloy.

 In a third embodiment according to the invention, the stack of

thin layers comprises three functional layers, each functional layer being separated from each other by a dielectric set of thin layers. This embodiment is shown diagrammatically in FIG. 3. The material 3000 comprises a transparent substrate 1001 and a first layer 1002 based on zinc nitride and tin and / or based on nickel nitride and chromium, said first layer 1002 being on and in contact with at least one of the surfaces 1001 a of the transparent substrate 1001. A 3001 stack of thin layers comprising three metallic functional layers

3004, 3008, 3012 is disposed on and in contact with the surface 1002a of said first layer 1002. The three metallic functional layers 3004, 3008, 3012 are separated from each other by a dielectric assembly 3006, 3010 of layers.

 In this third embodiment, the stack 3001 of thin layers also comprises a dielectric assembly 3002 between the first layer 1002 and the first metallic functional layer 3004, and a dielectric assembly 3014 of layers between the second metallic functional layer 30012 and the surface of the stack 3001 a.

 The stack 3001 may also include a so-called blocking layer

3005, 3009, 3013 disposed above and in contact with a metallic functional layer 3004, 3008, 3012. If it is necessary to protect each metallic functional layer 3004, 3008, it is advantageous that a blocking layer 3005, 3009, 3013 is arranged above and in contact with each metallic functional layer 3004, 3008, 3012 that comprises the stack 3001.

This layer is preferably based on the metals or alloys chosen from Ti and NiCr. Its thickness is generally equal to or less than 5 nm.

 It is also possible to have a blocking layer 3003, 3007, 3011 below and in contact with a functional metal layer 3004, 3008,

3012. If it is necessary to protect each metallic functional layer 3004, 3008, 3012, it may be advantageous for a blocking layer 3003, 3007, 3011 to be placed below and in contact with each metallic functional layer 3004, 3008 , 3012 which comprises the stack 3001.

It may be advantageous for certain applications that the entire stack 3001 includes a protective layer 3015 in order to protect it from possible physicochemical alterations by the atmosphere or the external environment with which it is susceptible. to be in touch. In this sense, the stack 3001 of layers may further comprise a layer of protection 3015 disposed above its surface likely to be in contact with the atmosphere. The physical thickness of said protective layer is generally equal to or less than 5 nm. By way of nonlimiting example, the protective layer may be a layer based on TiZr alloy.

 It is not required that the compounds included in the layers of the dielectric assemblies, in the blocking layers or in the protective layers, in particular those indicated in example, are perfectly stoichiometric. In particular, they may exhibit deviations from the stoichiometry for the contents of oxygen, nitrogen and / or other elements such as the doping elements.

 Preferably, the metallic functional layers of the stacks of thin layers are based on silver. [R8] Their physical thicknesses can advantageously be between 7 and 20 nm.

 When the material of the invention comprises a stack of layers

 thin which comprises at least one functional metallic layer, the physical thickness of the first layer can advantageously be between 0.5 and 10 nm, preferably between 0.5 and 8 nm.

 The transparent substrate according to the invention can be an inorganic substrate or

 organic, rigid or flexible, flat or curved. It will preferably be colorless, non-opaque and non-translucent in order to minimize the absorption of light and thus maintain maximum light transmission.

 Examples of organic substrates which can advantageously be

 used for the implementation of the invention are polymeric materials such as polyethylenes, polyesters, polyacrylates, polycarbonates, polyurethanes, polyamides. These polymers can be fluorinated polymers.

Examples of mineral substrates which can be advantageously used in the invention are the sheets of mineral or vitroceramic glass. The glass is preferably a glass of the silica-soda-lime, borosilicate, aluminosilicate or alumino-boro-silicate type. In a preferred embodiment of the invention, the transparent substrate is a sheet of soda-lime mineral glass.

 The material according to the invention can be used in monolithic, laminated or multiple glazing. In this sense, the invention also relates to a glazing unit comprising a material according to one of any of the embodiments described above.

 Monolithic glazing comprises a single sheet of glass. It is a simple glazing. When the material according to the invention is used as monolithic glazing, the first layer and possibly the stack of thin layers are preferably deposited on the face of the glass sheet oriented towards the interior of the room of the building on the walls of which glazing is installed. In such a configuration, it may be advantageous to protect the first layer and possibly the stack of thin layers against

 physical or chemical degradation using appropriate means.

 Multiple glazing comprises at least two parallel sheets of glass

 separated by an insulating gas slide. Most multiple glazings are double or triple glazing, that is to say that they comprise two or three glazing respectively. When the material according to the invention is used as an element of multiple glazing, the first layer and possibly the stack of thin layers are preferably deposited on the face of the glass sheet facing inwards in contact with the gas. insulating. This arrangement has the advantage of protecting the stack from chemical or physical degradation of the external environment.

Laminated glazing comprises at least two parallel sheets of glass

separated by an insert sheet. This interlayer sheet is generally an organic material, such as for example polyvinyl butyral (PVB). When the material according to the invention is used as an element of laminated glazing, the first layer and possibly the stack of thin layers can be deposited on any of the faces of the glass sheet, whether these faces are in contact with the sheet. interlayer or not. The deposition on the face of the glass sheet in contact with the interlayer sheet can be advantageous to protect it from chemical or physical degradation of the environment outside. However, care must be taken to ensure that the constituents of the interlayer sheet are not likely to interact with the layers of the stack and

 cause its degradation.

 Figure 4 schematically shows a cross section of a

 example of 4000 double glazing comprising a material according to the invention. In the figure, (E) corresponds to the outside of the room where the glazing is installed, and (I) inside the room. The glazing 4000 comprises a first glass sheet 4001 with an internal surface 4001 a and an external surface 4001 b, a second glass sheet 4002 with an internal surface 4002a and an external surface 4002b, an insulating gas plate 4004, a spacer 4005 and a sealing joint 4006. The glass sheet 4001 comprises, on and in contact with its internal surface 4001a in contact with the gas of the insulating gas blade 4004, a first layer based on zinc nitride and tin and / or nickel and chromium. The glass sheet 4001 may further comprise on and in contact with the first layer a stack of thin layers containing at least one functional metallic layer. The assembly composed of said first layer and said stack of thin layers is represented by the element 4003 in FIG. 4. The assembly 4003 is arranged so that its external surface 4003a which is opposite to that 4001 a of the sheet of glass 4001 is oriented towards the interior (I) of the room, for example a building or a vehicle, in which the glazing is used.

 Figure 5 schematically shows a cross section of an example of single glazing 5000 comprising a material according to the invention. On the face,

(E) corresponds to the outside of the room where the glazing is installed, and (I) inside the room. The glazing 5000 comprises a single sheet of glass 5001 with an internal surface 5001 a and an external surface 5001 b. The glass sheet 5001 comprises, on and in contact with its internal surface 5001a, a first layer based on zinc nitride and tin and / or nickel and chromium. The glass sheet 5001 can further comprise on and in contact with the first layer a

stack of thin layers containing at least one functional metallic layer. The assembly composed by said first layer and said stack of thin layers is represented by element 5003 in FIG. 5. The assembly 5003 is arranged so that its external surface 5003a which is opposite to that 5001 a of the glass sheet 5001 is oriented towards the interior (I) of the room, for example a building or a vehicle, in which the glazing is used.

 The invention also relates to a process for manufacturing a material with neutral optical properties having a chromatic neutralization function when it comprises stacks containing functional metallic layers.

 The method comprises the following steps:

 (a) the provision of a transparent substrate;

 (b) the deposition on and in contact of at least one of the surfaces of the transparent substrate with a first layer based on zinc nitride and tin and / or based on nickel nitride and chromium.

 The first layer based on zinc nitride and tin and / or based on

 Nickel and chromium nitride is deposited on the transparent substrate using conventional deposition methods known to those skilled in the art.

 In a preferred embodiment of the method of the invention, the deposition of the first layer based on zinc nitride and tin and / or based on nickel nitride and chromium is carried out using of a sputtering device assisted by a magnetic field of the magnetron type. An advantage of this embodiment is that it is easy to implement and suitable for many types of substrate.

 By way of nonlimiting example, when the deposition of the first layer based on zinc nitride and tin is carried out using a sputtering device assisted by a magnetic field of the magnetron type, it is possible to use the following conditions: a pressure of 2pbar, a frequency of 100kHz, a power of 250W, an Argon flux of 15 sccm (Standard Cubic Centimers per Minutes), a dinitrogen flux between 50 and 100sccm and a metal target based on tin and zinc with a tin to zinc mass ratio varying between 50:50 and 15:85.

By way of nonlimiting example, when the deposition of the first layer based on nickel nitride and chromium is carried out using a device for cathodic sputtering assisted by a magnetron-type magnetic field, it is possible to use the following conditions: a pressure of 2pbar, a frequency of 100kHz, a power of 250W, an Argon flux between 15 and 50sccm (Standard Cubic Centimers per Minutes), a nitrogen flux between 15 and 40sccm and a metallic target based on nickel and chromium with a nickel to chromium mass ratio varying between 50:50 and 80:20.

 Another advantage of the manufacturing process according to the invention is that it can be easily implemented in an existing installation of a physical deposition process for stacking thin layers. It can for example be implemented using an additional deposit module placed upstream of the installation or as a replacement for a module of the installation located upstream of said installation.

 In this sense, in one embodiment of the method of the invention, the

 the process can further comprise, after step (a), depositing on and in contact with said first layer a stack of thin layers comprising at least one functional layer based on silver.

 The effects and advantages of the invention are illustrated by the examples described below.

 Several examples of material according to the invention and several counterexamples have been produced. The values of several parameters making it possible to evaluate the optical and thermal performance of each example and counterexample were measured. These values were measured on a single glazing such as that illustrated in FIG. 5 or double glazing such as that illustrated in FIG. 4.

 The examples and counter-examples comprising a first layer 1001 and, optionally, a stack 2001, 3001, said first layer 1001 and said stack 2001, 3001 are deposited on one of the surfaces of the transparent substrate. The layer deposition conditions are those usually used by a person skilled in the art for a cathode sputtering assisted by a magnetic field (magnetron process), and widely documented in the literature, for example patent applications WO2012 / 093238 and

WO2017 / 00602. The targets that were used to deposit the first layer 1001 of the examples are a metallic target metal target based on nickel and chromium with a mass ratio nickel on chromium of 80:20 for when the first layer a layer based on nitride of nickel and chromium, and a metallic target at tin and zinc base with a tin to zinc mass ratio of 15:85 when the first layer is based on zinc and tin nitride.

 In the case of a single or double glazing, the parameters used to evaluate the optical and thermal performance of the examples and counterexamples are the following:

- T _L is the light transmission in the visible spectrum;

 - g, is the solar factor;

 - Rint is the value of the light reflection in the visible spectrum, expressed as a percentage, measured with an illuminant D65, a visual field of 2 ° for the observer on the internal surface 4002a, 5003a of the glazing;

- a ^* T and b ^* T are the values of the parameters a ^* and b ^* measured in transmission in the chromatic space L ^* a ^* b ^* CIE 1976 with an illuminant D65, a visual field of 2 ° for the observer and an angle of observation zero relative to normal to the surface of the glazing;

 - Rext is the value of the light reflection in the visible spectrum, expressed as a percentage, measured with an illuminant D65, a visual field of 2 ° for the observer on the external surface 4001 b, 5001 b of the glazing;

- a * Rext and b * Rext are respectively the values of the parameters a * and b * measured in reflection in the chromatic space L ^* a ^* b ^* CIE 1976 with an illuminant D65 and a visual field of 2 ° for the observer on the external surface 4001 b, 5001 b of the glazing;

- a * Rint and b * Rint are respectively the values of the parameters a * and b * measured in reflection in the chromatic space L ^* a ^* b ^* CIE 1976 with an illuminant D65 and a visual field of 2 ° for the observer on the internal surface 4002a, 5003a of the glazing.

The light transmission in the visible spectrum, T _L , the solar factor, g, and the selectivity, s, and the internal reflection, Rint, and the external reflection, Rext, in the visible spectrum are defined, measured and calculated. in accordance with standards EN 410, EN 613, ISO 9050 and ISO 10292. Color is measured in space chromatic L ^* a ^* b ^* CIE 1976 according to ISO 11664 with an illuminant D65 and a field of view of 2 ° for the reference observer.

 Two examples Ex1 and Ex2 corresponding to the first embodiment of the material of the invention illustrated in Figure 1 were made. They are described in Table 1. In these two examples, the transparent substrate 1001 is a first silica-soda-lime mineral glass, Glass 1, of the PLANICLEAR® type sold by Saint-Gobain Glass. In example Ex1, the first layer 1002 is a layer based on nickel nitride and chromium. In Example Ex2, the first layer 1002 is a layer based on zinc nitride and tin. In the two examples Ex1 and Ex2, the thickness of the first layer 1002 is 5 nm. Glass 1 has a thickness of 6 mm. In Table 1 are indicated the physical thicknesses, expressed in nanometers, of each of the layers.

 For comparison purposes, Table 1 includes a counterexample, CEx1, in which the substrate of the material does not comprise a first layer 1002. The transparent substrate has been replaced by a second silica-soda-lime mineral glass, Glass 2, of neutral color tinted in the mass of the SGG Parsol® type marketed by Saint-Gobain Glass. Glass 2 has a thickness of 6 mm.

 The values of the parameters used to evaluate the optical and thermal performance of the examples and counterexamples of table 1 are grouped in table 2.

 [Tables 1]

[Tables 2]

The values of the parameters TL, a ^* T, b ^* T, a ^* Rext and b ^* Rext of the example Ex2 and of the counterexample CEx1 are similar. The light transmission of the material of example 2 is slightly higher than that of the material of the counterexample CEx1. This shows that the material of the invention, when it comprises a first layer based on chromium and nickel nitride, makes it possible to obtain the same optical performance in terms of light transmission and color as a colored tinted glass. neutral.

 Example Ex1 shows that when the material of the invention comprises a first layer based on zinc nitride and tin, the values of the parameters * T, b * T, a * Rext and b * Rext are approximate those of the same parameters of the material of the counterexample CEx1. The material in Example Ex1 has a less neutral color than the material in Example Ex2. However, its light transmission is higher and the thickness of its first layer is at least twice as thin as that of the first layer of the material of Example 2. The material of Example Ex1 can be an advantageous compromise when high light transmission, a reduction in the thickness of the layers and a color close to neutrality in neutral reflection and in transmission are simultaneously sought.

 Four examples Ex3, Ex4, Ex5 and Ex6 corresponding to the second embodiment of the material of the invention illustrated in Figure 2 were made. They are described in Table 3. In these examples, the transparent substrate is a first silica-soda-lime mineral glass, Glass 1, of the PLANICLEAR® type sold by Saint-Gobain Glass. Glass 1 has a thickness of 6 mm.

In Examples Ex3 and Ex4, the first layer 1002 is a layer based on zinc nitride and tin. In Examples Ex5 and Ex6, the first layer 1002 is a layer based on nickel nitride and chromium. For comparison purposes, Table 3 includes a counterexample, CEx2, in which the substrate of the material does not comprise a first layer 1002. The transparent substrate is the same as that of Examples Ex3, Ex4, Ex5 and Ex6.

 In Examples Ex3, Ex4, Ex, Ex6 and the CEx2 counterexample, the transparent substrate further comprises on and in contact with said first layer 1002 a stack of thin layers comprising two functional metallic layers based on silver. . In Table 3 are indicated the physical thicknesses, expressed in nanometers, of each of the layers.

 The values of the parameters used to evaluate the optical and thermal performance of the examples and counterexamples of Table 3 are grouped in Table 4. These values were measured on double glazing

 including the materials of the example of examples Ex3, Ex4, EX5, EX6 and the counterexample CEx2. The 4000 double glazing has the following 6/16/4 structure: a sheet of soda-lime-silica glass 4001 with a thickness of 6 mm / a sheet of insulating gas 4004 with a thickness of 16 mm containing at least 90% d argon / a sheet of soda-lime-silica glass 4002 with a thickness of 4 mm. The first layer 1002 and the stack 3001 of thin layers is represented by the element 4003 in the figure. They were deposited on the inner surface 4001 a of glass sheet 4001 with a thickness of 6 mm.

 [Tables 3]

[Tables 4]

The values of the parameters a * T, b * T, a * Rext, b * Rext, a * Rint and b * Rint of the examples Ex3, Ex4, Ex5 and Ex6 are closer to zero than those of the parameters of the counter -example CEx2. This shows that the material of the invention has a chromatic neutralization function when it comprises stacks containing functional metallic layers. It therefore makes it possible to impart a neutral color to the stacks containing metallic functional layers.

 The physical thicknesses of the silver-based metallic functional layers of Examples Ex3 and Ex5 are lower than those of the same layers of the counterexample CEx2. The light transmission and internal and external reflection values are similar between these two examples and this counterexample. Compared to a material comprising a stack of thin layers which itself contains metallic functional layers and not comprising a first layer based on zinc nitride and tin and / or nickel nitride and chromium, the material of the invention therefore also makes it possible to reduce the physical thickness of the functional silver-based layers and to maintain the same performance in light transmission and reflection.

An example Ex7 corresponding to the third embodiment of the material of the invention illustrated in FIG. 3 has been produced. It is described in Table 5. In this example, the transparent substrate is a first silica-soda-lime mineral glass, Glass 1, of the PLANICLEAR® type sold by Saint-Gobain Glass. Glass 1 has a thickness of 6 mm. The first layer 1002 is a layer based on zinc nitride and tin. The transparent substrate comprises on and in contact with said first layer a stack 3001 of thin layers comprising three functional metallic layers based on silver. In Table 5 are indicated the physical thicknesses of each of the layers of the stack. They are expressed in nanometers.

 For comparison purposes, Table 5 includes a counterexample, CEx3, in which the substrate of the material does not comprise a first layer 1002. The transparent substrate is the same as that of Example Ex7.

 The values of the parameters used to evaluate the optical and thermal performance of Example Ex7 and counterexample of Table 5 are grouped in Table 6. These values were measured on double glazing

 including the materials of Example 7 and the CEx3 counterexample. The double glazing 4000 has the following structure 6/16/4: a sheet of soda-lime-silica glass 4001 with a thickness of 6 mm / a sheet of insulating gas 4004 with a thickness of 16mm containing at least 90% of argon / a sheet of silica-soda-lime glass 4002 with a thickness of 4 mm. The first layer 1002 and the stack 3001 of thin layers is represented by the element 4003 in the figure. They were deposited on the inner surface 4001 a of glass sheet 4001 with a thickness of 6 mm.

 [Tables 5]

[Tables 6]

The values of the parameters a ^* T, b ^* T, a ^* Rex, b ^* Rext, a ^* Rint and b ^* Rint of example Ex7 are closer to zero than those of the parameters of the counterexample CEx3. This again shows that the material of the invention has a chromatic neutralization function when it comprises stacks containing functional metallic layers.

Claims

Claims  [Claim 1] [Material comprising a transparent substrate which  comprises on and in contact with at least one of its surfaces a first layer based on zinc nitride and tin and / or based on nickel nitride and chromium.  [Claim 2] Material according to claim 1, such as the substrate  transparent further comprises on and in contact with said first layer a stack of thin layers comprising at least one layer  metallic functional.  [Claim 3] Material according to claim 2, such that said  thin film stack comprises two functional metallic layers separated by a dielectric set of thin layers.  [Claim 4] Material according to claim 2, such that said  thin film stack comprises three functional layers, each functional layer being separated from each other by a dielectric set of thin layers.  [Claim 5] Material according to any one of claims 2 to 4, such that the metallic functional layer or layers are based on silver.  [Claim 6] Material according to claim 5, such as thickness  physical or metallic functional layer (s) of silver is between 7 and 20 nm.  [Claim 7] Material according to any one of claims 2 to 6, such that the physical thickness of said first layer is between 0.5 and 8 nm.  [Claim 8] Material according to any one of claims 1 to 6, such that the physical thickness of said first layer layer is at least 2 nm. [Claim 9] Material according to any one of claims 1 to 8, such that said first layer is a layer based on zinc nitride and tin. [Claim 10] Material according to any one of claims 1 to 8, such that said first layer is a layer based on chromium and nickel nitride.  [Claim 11] Material according to any one of claims 1 to 10, such that the transparent substrate is a sheet of soda-lime mineral glass.  [Claim 12] Method for manufacturing a material with properties  neutral optics having a chromatic neutralization function, said method comprising the following steps:  (a) the provision of a transparent substrate;  (b) the deposition on and in contact of at least one of the surfaces of the transparent substrate with a first layer based on zinc nitride and tin and / or based on nickel nitride and chromium.  [Claim 13] The manufacturing method according to claim 12, such that said method further comprises, after step (a), depositing on and in contact with said first layer a stack of thin layers comprising at least one layer silver-based functional.  [Claim 14] Method of manufacturing a material according to  any one of claims 12 to 13, such that the deposition of the first layer based on zinc nitride and tin and / or based on nickel nitride and chromium is carried out using a sputtering device assisted by a magnetron-type magnetic field.  [Claim 15] Glazing comprising a material according to any one of claims 1 to 11. I