RU2734189C1 - Heat-resistant highly selective energy-saving silver coating on glass and method of its production - Google Patents

Abstract

FIELD: technological processes.

SUBSTANCE: invention relates to energy-saving coatings, in particular to energy-saving coatings on glass, having properties of thermal stability and high selectivity, and a method for production thereof. Disclosed is a heat-resistant highly selective energy-saving coating of silvery color on glass, consisting of separate directly contacting layers. Coating includes the following adhering layers in the order from the glass substrate to the outside: the first layer contains sub-stoichiometric nitride of aluminum-doped silicon Si-Al-N, the next layer contains tin-doped zinc oxide Zn-Sn-O, followed by a layer containing aluminum-doped zinc oxide Zn-Al-O, the next layer contains silver Ag, followed by a layer containing sub-stoichiometric nichrome oxide Ni-Cr-O, next layer contains aluminum-doped zinc oxide Zn-Al-O, followed by intermediate layer containing sub-stoichiometric aluminum nitride Al-N, the next layer contains tin-doped zinc oxide Zn-Sn-O, followed by a layer containing aluminum-doped zinc oxide Zn-Al-O, the next layer contains silver Ag, followed by a layer containing sub-stoichiometric nichrome oxide Ni-Cr-O, the next layer contains sub-stoichiometric tungsten nitride W-N, followed by a layer containing sub-stoichiometric aluminum nitride Al-N, the next layer containing tin-doped zinc oxide Zn-Sn-O.

EFFECT: technical result of the present invention is aimed at providing a combination of qualities of thermal stability, high selectivity and pronounced silver color of the energy-saving coating on glass substrates, expressed in an aggregate combination of a set of properties: resistance to prolonged effects of high temperatures, sun-proof properties with respect to thermal solar action with simultaneous maintenance of a satisfactory visible light transmission level, properties of energy efficiency by reduction of radiative heat losses during cold time and silver color of reflection from side of glass substrate, opposite to side, on which coating is applied, achieved in wide range of viewing angles.

4 cl, 6 dwg

Description

The present invention relates to energy-saving coatings, in particular to energy-saving coatings on glass, having the qualities of heat resistance and high selectivity, and a method for their production.

Thin-film optical coatings are applied on optically transparent substrates to change the intensity of the electromagnetic radiation arriving at them in a particular wavelength range due, for example, to its total or partial absorption or reflection. Thus, electrically conductive optical coatings, that is, coatings containing at least one metal layer with a low emissivity, are designed to weaken the transmission of infrared radiation. Currently, they are widely used as coatings applied to the surface of sheet architectural glass and glass used in the construction of various vehicles, and serve the purpose of reducing heat loss and controlling the flow of electromagnetic radiation from external sources, including solar radiation - as a complete spectrum, and its individual allocated ranges. Optical coatings typically include two or more different layers, each with a thickness ranging from less than 1 nm to more than 500 nm.

Known products with a coating applied to a glass substrate, the layer structure of which corresponds to the following generalized scheme: glass / lower dielectric layer or a set of successively applied lower dielectric layers / a layer of silver Ag or copper Cu / an upper dielectric layer or a set of successively applied upper dielectric layers, for example described in US patents No. 6605358, No. 6730352, No. 6802943, No. 7166359 and RF patents No. 2190692, No. 2563527, No. 2124483. These products have a lower emissivity compared to ordinary silicate glass and a low direct transmission in the far infrared range of the electromagnetic spectrum, due to which a decrease in heat loss from the room to the street in cold weather associated with the mechanism of transfer of thermal energy by radiation is realized. ... These products, however, do not provide a reduction in heat gain from thermal solar radiation, since they do not demonstrate a sufficient reduction in the direct transmission in the electromagnetic wavelength range corresponding to the thermal part of the infrared zone of the solar spectrum, and thus do not meet the energy saving criteria from the point in terms of energy efficiency of air conditioning in hot weather.

There are also known products of thin-film deposition on a glass substrate, the coating of which includes several layers of metal separated by ceramic layers, described, for example, in RF patent No. 2415968. Such products, often called highly selective, in addition to a lower emissivity compared to ordinary silicate glass, also have a low solar heat gain SHGC, due to a decrease in the transmission of electromagnetic radiation in the entire infrared range of wavelengths, while maintaining a relatively high level of visible light transmission. which is realized due to interference processes occurring during the successive overcoming of two nanoscale metal layers by radiation falling on the coating.

The described coatings can have, in combination with the desired energy efficiency properties, additional aesthetic qualities necessary from the point of view of means of architectural expressiveness, such as, for example, saturated color (for example, the reflected color of the glass surface). Examples of such products of thin-film optical sputtering on a glass substrate can serve as coatings described in patents of the Russian Federation No. 2563527 and US No. 7166359.

A separate requirement often imposed on thin-film coatings on glass substrates in general is their resistance to heat treatment. For example, thermally hardened glass panes with specified impact safety characteristics and / or thermally assisted bending glass panes are required for a large number of applications, for example, for building or automotive glazing, where requirements, for example, for impact safety characteristics can be are dictated incl. and industry standards and regulations. It is known that for thermal quenching and / or thermally-assisted bending of glass, it is necessary to ensure its thermal heating to temperatures around or above the softening temperature of the used glass melt, after which either quenching by rapid cooling of the glass blank or bending it is carried out using suitable bending means. ... The contemplated temperature range for carrying out the described processes for standard flat-polished soda-silicate float glass is typically about 530-710 ° C, with the glass panes being held in the specified temperature range for several minutes before starting the actual quenching and / or bending.

The terms "heat treatment", "heat treated", "heat resistant" and "heat treatable" in the following description and claims refer to methods of thermal bending and / or hardening, such as described above, as well as other heat-assisted processes, during which glass coated reaches temperatures up to about 780 ° C, inclusive, over a period of several minutes, such as up to about 15 minutes. Coated glass is considered to be heat treatable if it can withstand heat treatment without significant damage, with heat damage usually being high turbidity values of the coating surface - isotropic along the entire surface, or appearing locally as discrete areas or spots.

Of the known energy efficient thin film deposition products on a glass substrate, only a few meet the properties of resistance to heat treatment. Even fewer of them combine the qualities of simultaneously high selectivity, along with resistance to heat treatment. An example of such a product is the coating described in RF patent No. 2421419. Also, the choice of thin-film deposition products on glass is extremely limited, which simultaneously possess the properties of energy efficiency in relation to radiative heat loss, and resistance to heat treatment, along with a pronounced shade of reflection. An example of such a coating is described, for example, in RF patent No. 2477259. The heat-treated coated article described in this patent, however, does not show the desired shade over a wide range of viewing angles, but only when viewed from off-axis viewing angles, in particular at the declared viewing angle of 45 ° to the normal, which limits its use. Thus, the variety of shades of known heat-treatable products, combined with their level of energy efficiency in relation to radiative heat loss and / or heat gain, does not meet the demands of the current state of the architectural industry, especially in the case of highly selective heat-treatable products, the choice of products with a rich, highlighted outer color (from outdoor) reflections among which are currently extremely limited. In particular, there is a need to implement a heat-resistant product with a silvery shade of external reflection of the glass substrate surface from the side opposite to the side with the deposited energy-efficient thin-film optical coating, characterized by the following reflection hue parameters in the color quasi-coordinates a * / b * of the international standard CEILAB (D65 / 10 ° ): a * from -5 to -0.5, and b * from -5.2 to +2.5 ;.

Currently, in this area there is a need for a heat-resistant article with a coating on a glass substrate, which has the aggregate properties of high selectivity realized in it due to the combination of the specified sunscreen properties in relation to excessive solar thermal exposure and energy efficiency properties in terms of reducing radiative heat loss in cold weather. as well as the desired silver tint of reflection of the surface of the glass substrate from the side opposite to the side on which the thin-film energy-efficient optical coating is applied.

The closest to the claimed solution in terms of the totality of features is RF patent No. 2674417, which describes a coated product having a low emissivity coating with low visible light transmission, which can be used in an IC window unit for a gray appearance. The coated article comprises a substrate and a first layer containing silver and reflecting infrared (IR) radiation, a first layer containing a NiCr, a first silicon nitride-containing dielectric layer, a second NiCr-containing contact layer, a second layer containing silver and a reflecting infrared radiation, a second a NiCr-containing contact layer; and a second silicon nitride-containing dielectric layer. The second IR reflective layer is at least twice as thick as the first IR reflective layer. The coated article has a visible light transmittance measured on a monolith of not more than 55% and a reflectivity to visible light from the glass side, measured on a monolith, not more than 11%. The technical result consists in providing a coated article with low transmittance for visible light, low reflectance, good durability, desired (gray) color and thermal stability during heat treatment.

At the same time, according to the description of the preferred methods for obtaining the described article according to this invention, it is mentioned that it is preferable that each layer is deposited by sputtering in a vacuum, using one or more targets, if necessary (the targets for sputtering can be ceramic or metal) - since the deposited by spraying layers, incl. containing silicon nitride are in an amorphous state, that is, are amorphous both in the state after deposition and after HT (heat treatment), which contributes to the overall stability of the coating.

However, this coated article with thermal stability during heat treatment, and the aforementioned preferred method of its manufacture, do not allow to provide, along with a decrease in radiative heat loss from the room in cold weather, additional energy-efficient qualities of high selectivity, expressed in a reduced amount of solar heat gain with a simultaneous high transmission visible light and a low value of the surface ohmic resistance of the coating, which determines the level of the resulting emissivity of the product; and it is also prevented at the same time to achieve the desired silvery observation tint in external reflection from the side of the glass substrate opposite to the side to which the thin film coating is applied.

In addition, this coated product does not have a level of heat resistance satisfying the actual needs of its field of application: for example, the noted patent indicates that the thermal stability during heat treatment of the described coated product is such that its value ΔE * (when reflected from the glass side) as a result of TH (heat treatment) is not more than 5.0, and more preferably not more than 4.5, and most preferably not more than 4.1; however, it is also noted that the coated article has a low visible light transmittance of no more than 55%, more preferably no more than about 50%, more preferably no more than about 45%, and most preferably no more than about 40%, measured on monolith and / or in the IC block, and the allowable temperature of the heat treatment is at least 580 ° C, more preferably at least about 600 ° C, and even more preferably at least 620 ° C for the duration of the heat treatment 5-10 minutes or more. The latter indicates an excessively high turbidity of the coated substrate after exposure to temperatures above the order of several percent and not less than 1%, diffuse reflection from the outer side of the product (the side of the substrate opposite to the side on which the coating of the product installed in the IC window unit is applied) at which ensures the achievement of the specified range of ΔE * displacement by position in the colorimetric space of quasi-coordinates CEILAB at, at the same time, such low values of the transmission of visible light.

The technical result of the present invention is aimed at the simultaneous provision of: the qualities of heat resistance of the energy-saving coating on glass substrates, allowing the implementation of thermal hardening, heat-strengthening and thermally-assisted bending, and expressed in maintaining the value of the turbidity of the glass substrate with an energy-efficient coating after a temperature exposure at a level not higher than 9.8 ⋅10 ^-2 % at permissible exposure temperatures of at least 780 ° C for at least 15 minutes; as well as the silver color of the energy-saving coating on glass substrates in the case of light reflection from the surface of the glass substrate on the side opposite to the side on which the thin-film energy-efficient optical coating is applied, achieved in a wide range of viewing angles and characterized by the following reflection shade in color quasi-coordinates a * / b * international standard CEILAB (D65 / 10 °): a * from -5 to -0.5, and b * from -5.2 to +2.5; and high selectivity of an energy-saving coating on glass substrates, characterized by a selectivity S of not less than 1.384 with a corresponding transmittance of visible radiation T _{vis of} at least 42% and an emissivity of the product specified by the surface ohmic resistance of a thin-film coating not exceeding 2.6 Ohm /square.

The technical result is achieved by the fact that a heat-resistant, highly selective, energy-saving silver-colored coating on glass is proposed, consisting of separate directly contacting layers in the following order of listing from the glass substrate to the outside:

the first layer adjacent to the surface of the glass substrate contains a substoichiometric nitride of aluminum-doped silicon Si — Al — N;

the subsequent layer, which is the first contact layer, which contains oxide doped with tin zinc Zn — Sn — O;

it is followed by a layer containing aluminum-doped zinc oxide Zn-Al-O, which is the first catalytic layer;

the subsequent layer, which contains silver Ag, is the first infrared reflective layer;

followed by a layer containing substoichiometric nichrome oxide Ni-Cr-O, which is the first barrier layer;

the next layer, which contains aluminum-doped zinc oxide Zn-Al-O, is the first covering layer;

it is followed by an intermediate layer containing substoichiometric aluminum nitride Al-N;

the subsequent layer is the second contact layer and contains tin-doped zinc oxide Zn — Sn — O;

it is followed by a layer containing aluminum-doped zinc oxide Zn-Al-O, which is the second catalytic layer;

the subsequent layer, which contains silver Ag, is the second infrared reflective layer;

it is followed by a layer containing substoichiometric nichrome oxide Ni-Cr-O, which is the second barrier layer;

the next layer, which contains substoichiometric tungsten nitride W-N, is an absorbing layer;

it is followed by a layer containing substoichiometric aluminum nitride Al-N, which is the second covering layer, as well as a protective layer to provide chemomechanical protection of the entire previously listed layer structure;

the subsequent layer, which is the outer layer of the entire structure of the coating layers listed and plays the role of preventing the propagation of cracks "PRT" -layer, contains zinc-doped tin oxide Zn-Sn-O;

the thickness of the intermediate layer containing the substoichiometric aluminum nitride Al-N is from 57 nm to 68 nm, and the thickness of the layer containing the substoichiometric nitride of aluminum-doped silicon Si-Al-N is from 17 nm to 21 nm, with the thickness ratio layer containing substoichiometric aluminum-doped silicon nitride Si-Al-N to the total thickness of the second covering layer containing substoichiometric aluminum nitride Al-N and the outer layer containing zinc-doped tin oxide Zn-Sn-O is in the range from 0, 3 to 0.7, in addition, the total thickness of the two layers reflecting infrared radiation containing silver Ag is such that the resulting surface ohmic resistance of the heat-resistant highly selective energy-saving silver-colored coating on the glass does not exceed 2.19 Ohm / square, and the ratio of the thickness of the first layer, reflecting infrared radiation, containing silver Ag, to the thickness of the second layer reflecting infrared The light radiation containing silver Ag ranges from 0.21 to 0.38, while the ratio of the thickness of the first barrier layer, which contains the substoichiometric oxide of nichrome Ni-Cr-O, to the total thickness of the first contact layer, containing the oxide of tin-doped zinc Zn- Sn-O, and the first catalytic layer containing aluminum-doped zinc oxide Zn-Al-O, and the ratio of the thickness of the second barrier layer, which contains substoichiometric nichrome oxide Ni-Cr-O, to the total thickness of the second contact layer containing tin-doped zinc oxide Zn-Sn-O, and the second catalytic layer containing aluminum-doped zinc oxide Zn-Al-O are from 0.19 to 0.52, and the ratio of the thickness of the second barrier layer, which contains substoichiometric nichrome oxide Ni-Cr-O, to the thickness of the first barrier layer containing substoichiometric oxide of nichrome Ni-Cr-O is from 0.4 to 11.6, while the ratio of the thickness of the first contact layer containing the oxide is doped tin zinc oxide Zn-Sn-O, to the thickness of the first catalytic layer containing oxide doped with aluminum zinc Zn-Al-O, and the thickness of the second contact layer containing oxide doped with tin zinc Zn-Sn-O, to the thickness of the second catalytic layer containing aluminum-doped zinc oxide Zn-Al-O, range from 0.18 to 15.65, while the thickness of the absorbing layer, which contains substoichiometric tungsten nitride WN, is such that the resulting direct transmission of electromagnetic radiation in the range 385-790 THz of heat-resistant highly selective energy-saving silver-colored coating on glass is from 0.43 to 0.55, while the ratio of the thickness of the outer "PRT" -layer containing zinc-doped tin oxide Zn-Sn-O to the thickness of the first covering layer containing aluminum-doped zinc oxide Zn- Al-O is not less than 1.4, and the thickness of the outer "SPT" -layer containing zinc-doped tin oxide Zn-Sn-O is not less than 4 nm, while the total The thickness of the second covering layer, which contains the substoichiometric aluminum nitride Al-N, and the outer "PRT" -layer containing zinc-doped tin oxide Zn-Sn-O, is not less than 24 nm.

In addition, in a particular case, it is proposed to join a previously subjected to additional thermal hardening glass substrate with a multilayer coating applied to its surface with at least one additional transparent substrate facing the outer coating layer containing zinc-doped tin oxide Zn-Sn-O.

In addition, in another case, it is proposed to join a preliminarily heat-hardened glass substrate with a multilayer coating applied to its surface with at least one additional transparent substrate facing the outer coating layer containing zinc-doped tin oxide Zn-Sn-O.

Ensuring the achievement of the technical result by obtaining a coating of the required properties is carried out by implementing a method for obtaining a heat-resistant, highly selective, energy-saving silver-colored coating on glass, including applying in a vacuum chamber directly to the surface of the glass base from one of its sides contacting layers by spraying materials in a magnetron discharge plasma cathode targets in the following sequence:

bi-metal alloy of silicon doped with aluminum SiAl with a degree of doping ranging from 2% to 60%;

bi-metal alloy doped with tin zinc ZnSn with an alloying degree of 5% to 80%;

bi-metallic alloy alloyed with aluminum zinc ZnAl with a degree of alloying ranging from 5% to 80%;

silver Ag with an impurity purity of at least 90%;

bi-metallic alloy of nichrome NiCr with a partial concentration of nickel not less than 10%;

ceramic stoichiometric oxide of a bi-metallic alloy alloyed with aluminum zinc ZAO with a degree of alloying from 5% to 80%;

aluminum Al with an impurity purity of at least 84%;

bi-metal alloy doped with tin zinc ZnSn with an alloying degree of 5% to 80%;

bi-metallic alloy alloyed with aluminum zinc ZnAl with a degree of alloying ranging from 5% to 80%;

silver Ag with an impurity purity of at least 90%;

bi-metallic alloy of nichrome NiCr with a partial concentration of nickel not less than 10%;

tungsten W with an impurity purity of at least 93%; aluminum Al with an impurity purity of at least 84%;

bi-metal alloy doped with tin zinc ZnSn with an alloying degree of 5% to 80%;

the burning voltage of the magnetron discharge during sputtering of cathode targets made of a bi-metal alloy doped with aluminum silicon SiAl and aluminum Al is maintained in the range from 420 to 560 V, when sputtering cathode targets from a bimetallic alloy doped with tin zinc ZnSn and from a bi-metal alloy doped with zinc aluminum ZnAl - in the range from 420 to 510 V, when sputtering cathode targets from a bi-metallic alloy of nichrome NiCr and tungsten W - in the range from 550 to 610 V, when sputtering cathode targets made of silver Ag, the burning voltage of a magnetron discharge does not exceed 480 B, and when sputtering cathode targets from a ceramic stoichiometric oxide of a bi-metallic alloy doped with aluminum zinc ZAO, the combustion voltage of the magnetron discharge is maintained at least 600 V; in this case, the discharge current does not exceed the following limits: for cathode targets made of a bi-metallic alloy doped with aluminum silicon SiAl no more than 110 A, for cathode targets made of aluminum Al no more than 160 A, for cathode targets made of a bi-metallic alloy doped with tin zinc ZnSn not more than 60 A, for cathode targets made of a bi-metallic alloy doped with aluminum zinc ZnAl no more than 90 A, for cathode targets made of a bi-metallic alloy nichrome NiCr, tungsten W and ceramic stoichiometric oxide bimetallic alloy doped with aluminum zinc ZAO - no more than 90 And, for cathode targets made of silver Ag is not more than 15 A; wherein the combustion magnetron sputtering under plasma discharge is maintained in the pressure range from 1,7⋅10 ^-3 to 4⋅10 ^-2 mbar for all cathode target materials, and acts as the working gas, argon Ar, and the spray target from bi- a metal alloy doped with tin zinc ZnSn, a bi-metal alloy doped with aluminum zinc ZnAl and a bi-metallic alloy of nichrome NiCr, a reaction gas component is additionally admitted into the vacuum chamber, which is oxygen O ₂ , and the ratio of the amount of gas supply of oxygen O ₂ to the value of the gas supply of argon Ar does not exceed 1.65, and when sputtering targets from a bi-metallic alloy doped with aluminum silicon SiAl, from aluminum Al and from tungsten W, a reaction gas component is additionally admitted into the vacuum chamber, which is nitrogen N ₂ , and the ratio of the amount of nitrogen gas injection N ₂ to the value of the argon gas injection flow Ar is maintained in such a way that so that the ratio of the intensity of the characteristic radiation of ionization of the sputtering component of the working gas mixture, which is argon Ar, to the intensity of the characteristic radiation of ionization of the main metal component of the target in the case of a bimetallic alloy of aluminum-doped silicon SiAl, which is silicon Si, and the target metal, in the case of monometallic targets made of aluminum Al and tungsten W, respectively, did not exceed 43.

The use of substoichiometric aluminum-doped silicon nitride Si-Al-N as the first layer of a heat-resistant energy-saving coating is due to the combination of the following qualities manifested by this material and the requirements for the qualities displayed by the product. It is known that this material has a high degree of adhesion to the surface of the glass substrate due to the so-called. the effect of "crosslinking" with crystalline precipitates of short-range order of the quasi-amorphous structure of the glass melt through free chemical bonds of silicon atoms with the formation of, predominantly, covalent polar bonds, which is necessary to ensure reliable retention of subsequent deposited layers on the substrate surface. In addition, aluminum-doped silicon nitride Si-Al-N belongs to the group of materials that help prevent crack propagation (CRT), consisting of oxides or nitrides of metals or metal alloys selected from the group consisting of Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W. As a rule, PRT materials suppress crack propagation in the brittle, glassy outer layer of various optical coatings during industrial post-processing for the manufacture of insulating glass assemblies. In the present invention, the use of the above material as the first layer adjacent to the surface of the substrate helps to prevent mechanical degradation and delamination of the infrared reflecting layers containing silver Ag, thus achieving the desired sunscreen properties in relation to excessive solar thermal exposure, as well as energy efficiency qualities with the point of view of reducing radiative heat loss in cold weather, corresponding to the value of the emissivity of the product, set by the surface ohmic resistance of the thin-film coating, not exceeding 2.19 Ohm / square. The deposition of a thin-film layer in the form of a substoichiometric nitride is necessary to ensure its barrier properties associated with a reduced diffusion coefficient through the deposited layer of components from the substrate, which, as a rule, acquire increased diffusion mobility with thermal energy during heating of the substrate during heat treatment - mainly sodium, magnesium, calcium and their oxides. This, in turn, prevents the entry of the above radicals to the layers of reflecting IR radiation of silver Ag, due to which both the defoliation of the coating layers, provoked by the release of induced stresses, as a whole, and the local aggregation of conductive thin-film optical coating, due to which degradation of the thin-film coating will be observed during heat treatment, expressed in its cloudiness. Finally, it has been experimentally shown that the use of aluminum as the alloying metal component of the first layer, adjacent to the surface of the glass substrate, exhibiting the PRT quality, from the entire group of suitable metals, consisting of Ti, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, contributes to the additional formation of the most stable bonds with the subsequent deposited first contact layer containing tin-doped zinc oxide Zn-Sn-O, the reasons for choosing which as the first contact layer and the need to use it as a layer in overall are given below. The latter ensures the maintenance of a high level of adhesion at the boundary of individual layers of the thin-film coating of the product, which is necessary to ensure its structural integrity and mechanical resistance to external influences during use.

At the same time, the use of a subsequent layer containing tin-doped zinc oxide Zn-Sn-O is necessary to ensure stable contact between the first layer of substoichiometric aluminum-doped silicon nitride Si-Al-N adjacent to the glass substrate surface, and the subsequent group of the IR-reflecting layer, consisting of a first catalytic layer containing aluminum-doped zinc oxide Zn-Al-O, immediately a first infrared reflecting layer containing silver Ag, and a subsequent layer containing substoichiometric nichrome oxide Ni-Cr-O, which is the first barrier layer ... It is generally accepted to call layers that perform the indicated functions of ensuring stable contact and accompanying adhesion, contact layers. The choice of tin-doped zinc oxide Zn-Sn-O as a specific material is associated with maintaining a minimum difference in the refractive index of this layer with the refractive index of the subsequent catalytic layer containing aluminum-doped zinc oxide Zn-Al-O, which, in turn, leads to the development of layer of the so-called the "antireflection effect", when the reflective surface is covered with a non-reflective film to split the beam of the incoming radiation due to the fact that the absorption of light in the film is very small compared to the semitransparent layers of the subsequent deposited thin-film metal (in this case, layers of reflective IR silver Ag) as a result, it becomes possible to further minimize the distortion of the split beam when passing through the barrier metal layer and to achieve the desired increased transparency of the product in relation to the wavelengths of the visible part of the solar spectrum of electromagnetic radiation.

In this case, the need for a subsequent layer of oxide doped with aluminum zinc Zn-Al-O, as well as the choice of this particular layer material, are associated with the fact that the oxide of this alloy belongs to the group of materials that contribute to the formation of uniformly homogeneous layers of noble metals on top of them, incl. hours, which is relevant in this particular case, silver. This, in turn, contributes, along with ensuring a stable contact between this layer and the first contact layer deposited in front of it, containing zinc-doped zinc oxide Zn-Sn-O, catalysis of the uniform growth of the electroconductive metal layer of silver Ag, which is the first reflective IR - radiation by a layer, which makes it possible to achieve the qualities of energy efficiency of the product in terms of reducing radiative heat losses in cold weather, corresponding to the value of the emissivity of the product, set by the surface ohmic resistance of the thin-film coating, not exceeding 2.19 Ohm / square, due to the structural homogeneity of the reflective IR radiation of the electrically conductive layer of silver Ag due to the concomitant minimization of parasitic resistance at the boundaries of crystalline conglomerates of a thin-film silver layer with a catalyzed layer of Zn-Al-O, reducing the amount of the latter. In general, the group of materials exhibiting the described catalytic properties includes bimetallic zinc oxides Zn doped with an element of the group of light metals such as aluminum Al and tin Sn. Also, alternatively, it is possible to use bimetallic oxides of indium alloys In, doped with an element of the group of light metals, such as aluminum Al or tin Sn, as the catalytic layer. However, it was empirically found that only the use of a thin-film layer of zinc oxide doped with aluminum Zn-Al-O from the entire group of listed materials as catalytic with respect to the reflecting IR-radiation layer of silver Ag provides an optimally high preservation of its catalytic qualities, incl. and according to the results of heat treatment of the product. At the same time, its contact properties with respect to the first layer of substoichiometric nitride of silicon doped with aluminum Si-Al-N adjacent to the surface of the glass substrate demonstrated degradation during heat treatment, expressed in defoliation of the layer with subsequent delamination of the entire thin-film structure deposited on top of it. This effect, on the contrary, was not observed for the case of using the first layer of substoichiometric nitride doped with aluminum silicon Si-Al-N, a layer of tin-doped zinc oxide Zn-Sn-O, which is adjacent to the glass substrate surface. At the same time, the mutual adhesion of a pair of successively deposited layers of oxide doped with tin zinc Zn-Sn-O and doped with aluminum zinc Zn-Al-O is quite high and also persists during thermal exposure. As a result of the aforementioned empirical observations, a sequence of functionally separated contact and catalytic layers, pre-deposited by the IR-reflecting silver layer of Ag, which are tin-doped zinc oxide Zn-Sn-O and aluminum-doped zinc oxide Zn-Al-O, respectively, demonstrated an optimal combination of of the above functional requirements for these layers, persisting incl. and in the course, in accordance with the formulation of the technical problem solved by the present invention, heat treatment of the described product.

The subsequent IR reflective layer contains silver Ag. In this invention, metallic silver Ag was chosen as the material of the IR reflecting layers due to the combination of absorption and reflection qualities of electromagnetic radiation in the middle and far infrared wavelengths of the infrared part of the spectrum inherent in thin-film layers of this material, corresponding to the combination of its refractive index and extinction coefficient. (in particular, constituting, respectively, 0.135 and 3.985 for a wavelength of the order of 632.8 nm), which provides the product with the required low-emission qualities, such as low surface resistance and corresponding emissivity.

To realize the quality of the sun-protection properties of the product in relation to excessive thermal solar exposure, the subsequent layer structure of the thin-film coating of the product is performed according to the scheme of a highly selective platform with two layers included in the coating, reflecting IR radiation and containing silver, separated by ceramic layers. Due to a decrease in the transmission of electromagnetic radiation in the entire infrared range of wavelengths, along with maintaining a relatively high level of transmission of visible light, which is realized due to interference processes occurring during the successive overcoming of two nanosized layers of silver Ag by radiation falling on the coating, the described product, in addition to the reduced In comparison with ordinary silicate glass, the emissivity also has a high selectivity S, which, in turn, ensures the manifestation of sun-protection properties in relation to excessive thermal solar exposure, characterized by a low coefficient of direct solar radiation transmittance T _sol . Since the chosen scheme for constructing a thin-film optical energy-saving coating of an article assumes a repetition of the general structure of sequentially following materials in the case of IR reflecting layers containing Ag silver and surrounding dielectric layers, for convenience of designation, the silver reflecting layers are called the first and second, respectively. their order from the surface of the optically transparent glass substrate to the outside, and a similar naming convention is also used for layers adjacent to silver layers.

Oxygen diffusion barrier layers consisting of so-called oxygen scavenger materials, the group of which includes metals and alloys of such metals as Ti, Ni, Cr, In and Sn, as well as their oxides, deposited on top of functional IR-reflecting layers of heat-resistant optical coatings on glass substrates, prevent the penetration of high-energy reaction elements before total - oxygen, to the functional layers in the course of providing high diffusion mobility of the reaction gas components chemisorbed by the coating surface, temperature processes, due to which the stability of both the functional IR-reflecting layers and the entire layer structure of the coating as a whole is realized in relation to thermal processing. In the context of the present invention, as the first and second barrier layers applied directly over the first and second infrared reflecting layers containing silver Ag, respectively, layers containing substoichiometric nichrome oxide Ni — Cr — O were selected. In this case, the choice of nichrome oxide Ni-Cr-O as the material of the barrier layers is due to a combination of two factors: the provision, as noted above, by this material of the necessary qualities of oxygen absorption, contributing to the implementation of the thermal stability of the described coating on glass declared within the technical problem of the present invention, as well as optical qualities of this material - as a balance of its refractive indices and extinction - allowing to achieve within the range of thicknesses within which the deposition of the first and second barrier coating layers containing substoichiometric oxide of nichrome Ni-Cr-O should be maintained, for the reasons described below, minimization the effect of the contribution of parasitic absorption in the visible wavelength range of electromagnetic radiation from interference effects on groups of layers adjacent to functional IR-reflective layers of silver Ag, namely: a contact layer that contains oxide doped with tin zinc Zn-Sn-O; a catalytic layer containing oxide doped with aluminum zinc Zn-Al-O; directly the barrier layer containing substoichiometric oxide of nichrome Ni-Cr-O, and the covering layer, which contains oxide doped with aluminum zinc Zn-Al-O. The latter contributes to the possibility of achieving the claimed in the technical problem of the present invention the aggregate of the selectivity level of the thin-film optical coating on the glass substrate S and the value of the integral super-transmission of visible radiation T _vis in the range of not less than 1.384 and 42%, respectively. In turn, the deposition of the material in the form of a substoichiometric oxide is also due to two factors. First, the oxygen deficiency in the layer contributes to the maximization of the barrier properties in relation to oxygen diffusion, since it is energetically more favorable for oxygen atoms to maintain their position in the layer structure, being fixed in the barrier layer through the formation of chemical bonds with the atoms of its constituent material, than to a greater extent the layer is undersaturated with the reaction gas components preliminarily to the heat treatment of the article. Second, it is known in the art that the adhesion of the oxygen-containing barrier layer to the silver-containing infrared-reflecting functional layer is the higher, the more the barrier layer is metallic in the vicinity of the side of the silver-containing functional layer external to the glass substrate. The use of a barrier layer in the form of a pure metal outside the substoichiometric inclusion of oxygen, however, is not possible within the framework of the task of implementing the technical result of the present invention, since active oxidation during heat treatment of all metal barrier layers leads, along with a significant increase in light transmission, to a significant and clearly visible a change in the color of the coated glass, as a result of which the ability to provide the required saturated silvery shade of the product is lost in the case of light reflection from the surface of the glass substrate from the side opposite to the side on which the thin-film energy-efficient optical coating is applied, achieved in a wide range of viewing angles and characterized by the following reflection shade parameters in color quasi-coordinates a * / b * of the international standard CEILAB (D65 / 10 °): a * from -5 to -0.5, and b * from -5.2 to 2.5.

The need to use the so-called covering layer applied after the barrier layer containing the substoichiometric oxide of nichrome Ni-Cr-O is caused by the requirement to protect the oxygen-free and deposited under conditions of oxygen deficiency layers of silver Ag and nichrome, respectively, from partial or complete destruction upon contact with oxygen-containing radicals during the subsequent deposition of oxidized dielectric layers of a thin-film optical energy-saving coating during the reaction interaction with oxygen and the formation of a porous structure, which, in turn, leads to a sharp decrease in the transmittance of visible light and a decrease in the reflection coefficient in the infrared region of the spectrum. The covering layer should also be partially barrier with respect to oxygen diffusion in the direction of the conductive metal layers, in this case a silver layer reflecting IR radiation, to the extent that it inhibits oxygen diffusion during the deposition of the layers deposited after it into the depth of the previously deposited part of the layer structure. , and consist of another, less active metal, oxidized in order to minimize the final additional decrease in the coefficients of translucency and heat reflection. Similarly, in order to minimize the final additional decrease in the coefficients of transparency and heat reflection of the product, this layer should consist of a material that is as close as possible in terms of its refractive index and extinction coefficient to the previous contact layer, counting from the substrate outward. Based on the above criteria, as the material of the first covering layer of the thin-film optical energy-saving coating of the product, we chose an oxide of aluminum-doped zinc Zn-Al-O, which meets the above requirements.

At the same time, to ensure the effect of spectral broadening, which makes it possible to achieve the required shade of external reflection of the product, along with the preservation of the effect of interference reradiation between the conductive metal layers reflecting with respect to IR radiation, the dual highly selective structure of building a thin-film coating of the product in the form of two successive series of layers "contact layer - catalytic layer - IR-reflecting silver layer - barrier layer "is separated by a sufficiently thick optically transparent dielectric layer, commonly referred to as an intermediate layer, the thickness of which in the general case is several tens of nanometers, depending on the degree of spectral broadening to be achieved. Within the framework of the present invention, based on the following conditions, the substoichiometric aluminum nitride Al-N was chosen as the material of the intermediate layer. The choice of aluminum as a metal component of the specified substoichiometric nitride is due to the best adhesion of the resulting material to the aluminum-containing surrounding near-silver layers, i.e. the first covering layer containing aluminum-doped zinc oxide Zn-Al-O on the side of the optically transparent glass substrate, and the second contact layer containing tin-doped zinc oxide Zn-Sn-O, on the other hand, outer relative to the optically transparent glass substrate, behind due to the formation of aluminum-aluminum metal bonds. At the same time, as has been empirically shown, the use of this metal component of the layer material helps to maximize, for the above range of thicknesses of this layer, the reasons for choosing which will be given below, the spectral broadening function of the entire resulting layer structure when external electromagnetic radiation passes through it. At the same time, the use of a layer in the form of a substoichiometric nitride provides this layer with the necessary barrier properties associated with a reduced diffusion coefficient through the deposited layer of reaction components from the overlying layers external to this layer relative to the substrate, as a rule, acquiring an increased diffusion coefficient, which is characteristic of substoichiometric aluminum nitrides. mobility with thermal energy during heating of the substrate during heat treatment - primarily, oxygen atoms from oxide layers. This, in turn, prevents the flow of reaction radicals to the layer of silver Ag reflecting infrared radiation of silver, which lies below the intermediate layer of substoichiometric aluminum nitride Al-N, due to which both defoliation of the coating layers, provoked by the release of induced stresses, as a whole, and local, initiated by reaction processes on diffusing radicals, aggregation of conductive layers of a thin-film optical coating, due to which degradation of a thin-film coating will be observed during heat treatment, expressed in its cloudiness.

As noted above, in order to realize the qualities of the highly selective product, the layer structure of the thin-film coating of the product is performed according to the platform scheme with two layers included in the coating, reflecting IR radiation and containing silver, separated by ceramic layers. For this reason, the chosen scheme for constructing a thin-film optical energy-saving coating of an article assumes a repetition of the general structure of sequentially following materials in the case of IR reflecting layers containing silver Ag and surrounding dielectric layers. To minimize the effect of reducing the transparency coefficient of the product by increasing the total total thickness of electrically conductive metal layers absorbing electromagnetic radiation in the visible range of wavelengths, in the role of which in the layer structure of a heat-resistant highly selective energy-saving silver-colored coating on glass there are two reflective IR-radiation layers of silver Ag, the second contact layer, the second catalytic layer, the second IR reflecting layer, the second barrier layer and the second covering layer should consist of materials that are as close as possible in their refractive indices and extinction coefficients to the first contact layer, the first IR reflecting layer and the first covering layer respectively. In addition, the second contact layer of the coating must ensure reliable adhesion of the entire repeating structure of the second reflective IR-radiation layer and the surrounding dielectric layers - the second contact and second catalytic layers on the side of the optically transparent glass substrate and the second barrier layer on the side opposite to the location of the optically transparent glass substrate - to the already deposited part of the structure of thin-film coating layers. Based on the above requirements for the materials of the repeating structure - the second reflective IR-radiation layer and the surrounding second contact, second catalytic and second barrier dielectric layers - as materials of the second contact, second catalytic, second reflective IR-radiation and the second barrier layers were selected materials , constituting the corresponding, previously following, if we consider from the side of the glass substrate, the layers of the first part of the repeating highly selective structure of the thin-film heat-resistant energy-saving coating - the first contact, the first catalytic, the first reflective IR radiation and the first barrier layers: as a material of the second contact layer applied over and in direct contact with the previous with respect to the surface of the glass substrate intermediate layer containing substoichiometric aluminum nitride Al-N, tin-doped zinc oxide Zn-Sn-O is used; the material of the subsequent second catalytic layer is aluminum-doped zinc oxide Zn — Al — O; silver Ag is used as the material of the next second IR reflecting layer; Substoichiometric Ni-Cr-O nichrome oxide is used as the material of the next layer, which is the second barrier layer.

The need to include an absorbing layer in the layer structure of the described coating, which is a layer of substoichiometric tungsten nitride WN, is due to the fact that, since during the heat treatment of the product, oxygen diffusing through the layer structure of the coating is retained and saturated with oxygen, barrier materials-oxygen absorbers selected in as materials of a layer structure to protect an article from degradation during heat treatment when oxygen atoms reach from the atmosphere and nearby oxide layers, as well as reaction radicals from the substrate, conductive functional IR reflecting silver layers Ag and adjacent catalytic layers, the layer structure of the coating collectively demonstrates the resulting increase in the transmittance in relation to the visible range of wavelengths of electromagnetic radiation with an accompanying, often significant, shift in position along the color quasi-coordinates a * / b * of the CEILAB standard (D65 / 10 °) colorimetry in s wind reflection from the surface of the glass substrate from the side opposite to the side on which the thin-film energy-efficient optical coating is applied, reaching over 10 units along each axis of the two-dimensional colorimetric quasi-space. As a result, in order to minimize the specified effect, and in order to control the level of displacement of the balance of light transmission / absorption of the layer structure of the coating as a result of heat treatment in a range that makes it possible to achieve the desired saturated silver hue of light reflection from the side opposite to the side on which the thin-film energy-efficient optical coating is applied, a wide range of viewing angles, as well as for adjusting the value of the displacement of the position according to the color quasi-coordinates a * / b * of the CEILAB standard (D65 / 10 °) colorimetry of the light reflection of the product during heat treatment, after the second layer group of highly selective energy-efficient thin-film construction, consisting of the second IR-reflective silver layer and adjacent second contact, second catalytic and second barrier layers, directly over the second barrier layer containing substoichiometric nichrome oxide Ni-Cr-O, is applied providing excessive absorption in the form of In the range of wavelengths of electromagnetic radiation, a layer, the material of which in the framework of the present invention was chosen substoichiometric tungsten nitride W-N, and which is traditionally called an absorbing layer. The choice of tungsten as a metal component of the material of the absorbing layer is due to the fact that this metal has optimal optical characteristics in terms of the balance of refractive index and extinction coefficient, reaching values of 3.774 and 2.634 units at a wavelength of 0.77 μm, respectively. Due to this, when using tungsten as a metal component of the material of the absorbing layer, the optimal level of the required absorption in the visible part of the spectrum of electromagnetic radiation is achieved already at the thicknesses of the absorbing layer, which will be small enough to avoid a significant stepwise decline in the light transmission of the product, including during its heat treatment, due to the occurrence of parasitic processes of an interference nature when electromagnetic radiation overcomes the entire set of layers of a thin-film structure. At the same time, the effect of compensation for spectral broadening is also realized in the wavelength range of the order of 380-810 nm, due to which the inclusion of a layer of this material in the layer structure of the coating does not directly distort the behavior of the spectral transmission and reflection curves of the product, during the accompanying stabilization of the position in terms of color. quasi-coordinates a * / b * of the CEILAB standard (D65 / 10 °) colorimetry of light reflection in light reflection from the surface of the glass substrate on the side opposite to the side on which a thin-film energy-efficient optical coating of the product is applied during heat treatment. At the same time, the deposition of the layer in the form of a substoichiometric nitride provides this layer with the necessary barrier qualities associated with a reduced diffusion coefficient through the deposited layer of reaction components from the overlying layers external to this layer relative to the substrate, which usually acquire increased diffusion mobility, which is characteristic of substoichiometric tungsten nitrides. with thermal energy during the heating of the substrate during heat treatment - first of all, oxygen atoms coming from the atmosphere during the heat treatment.

The second covering layer, applied directly over the absorbing layer of substoichiometric tungsten nitride WN, and containing substoichiometric aluminum nitride Al-N, is necessary in connection with the requirement to protect the oxygen-free and deposited under oxygen deficiency second layers of silver Ag and nichrome, respectively, from partial or complete destruction at contact with oxygen-containing radicals and the formation of a porous structure as a result of this contact, which, in turn, leads to a sharp decrease in the transmittance of visible light and a decrease in the reflection coefficient in the infrared region of the spectrum. In this case, the second covering layer must contain an effective barrier material with respect to oxygen diffusion in the direction of the conductive metal layers in order to ensure the inhibition of oxygen diffusion during heat treatment into the depth of the previously deposited part of the layer structure. In addition, it should be composed of a material having a refractive index n of the order of 1.8 to 2.3 so as not to have a negative minimizing effect on the qualities of the "antireflection effect" exhibited by the first layer adjacent to the surface of the glass substrate of the article. containing a substoichiometric nitride of silicon doped with aluminum Si-Al-N, due to the fact that the absorption of light in a thin-film layer of Si-Al-N is extremely small in comparison with semitransparent layers of the subsequent deposited thin-film metal, during the passage of electromagnetic radiation of the visible wavelength range through the entire the thickness of the thin-film layer structure of a heat-resistant, highly selective, energy-efficient coating of an article applied to an optically transparent glass substrate. Similarly, in order to minimize the final additional decrease in the coefficients of transparency and heat reflection of the product, this layer should consist of a material that is as close as possible in terms of its refractive index and extinction coefficient to the intermediate layer containing the substoichiometric aluminum nitride Al-N. Based on the above criteria, as the material of the second covering layer of the thin-film optical energy-saving coating of the product, a material similar to that used to form the intermediate layer, substoichiometric aluminum nitride Al-N, was chosen. In addition to the fact that the layer of this material meets the above requirements, it also, as it was empirically determined, provides, with a layer thickness that is in the permissible range of values, the reasons for establishing which are described below, effective mechanical, and also, due to its barrier properties, chemical protection of the entire structure of previously applied layers of thin-film optical energy-saving coating of the product. For this reason, this layer, in addition to the fact that it plays the role of the second covering layer, is also a protective layer at the same time to provide chemomechanical protection of the entire previously listed layer structure. At the same time, however, it does not exhibit the required level of crack propagation prevention (CRT) qualities necessary for proper protection of the product layer structure from crack propagation during the initial concentration and subsequent stress relaxation at the boundaries of individual layers of individual materials during heat treatment processes. associated with a sharp change in the temperature of the substrate, for example, during thermal hardening, which consists in rapid heating and subsequent sharp cooling of the product.

For this reason, to prevent the propagation of cracks and the associated mechanical damage to the entire structure of the previously described layers of the thin-film optical energy-saving coating of the product, an outer "PRT" layer is applied over them, containing oxide of zinc-doped tin Zn-Sn-O. The choice of Zn-Sn-O as the outer layer material is based on the following requirements related to the functional properties of this layer. This layer should have the required properties of preventing crack propagation (CRT) with respect to the part of the layer structure of the coating deposited before it during the relaxation of internal stresses induced by the described layer structure during heat treatment processes, and, accordingly, consist of metal oxides or metal alloys of the selected from the group consisting of Ti, Zn, Sn, In, Zr, Cr, Nb, and Ta. The choice of zinc as the main metal component of the specified oxide of the bimetallic alloy is due to optimal adhesion while ensuring the required "PRT" -quality of the resulting material to the aluminum-containing second covering layer of the second silver layer reflecting infrared radiation. Finally, the outer layer should, along with the above requirements, have an extinction coefficient k of the order of 1.9 to 2.1 with a refractive index n in the range from 2.01 to 2.08, so as not to have a negative minimizing effect on quality. " antireflection effect ", manifested by the first layer adjacent to the surface of the glass substrate of the product, and containing substoichiometric nitride of silicon doped with aluminum Si-Al-N, due to the fact that the absorption of light in the thin-film layer of Si-Al-N is very small compared to semitransparent layers the subsequent deposited thin-film metal, in the course of the passage of electromagnetic radiation of the visible range of wavelengths through the entire thickness of the thin-film layer structure of a heat-resistant highly selective energy-efficient coating of the product, applied to an optically transparent glass substrate; and also to implement the effect of shifting the reflection spectrum of the product from the side of the glass substrate, opposite to the side on which the thin-film energy-efficient optical coating is applied, in the visible range of electromagnetic radiation wavelengths to the region of the order of 390-780 nm through appropriate adjustment of the individual thicknesses of the group of layers adjacent to the first and second functional layers of silver Ag within the values described below - namely: first and second contact, catalytic and barrier layers containing tin-doped zinc oxide Zn-Sn-O, aluminum-doped zinc oxide Zn-Al-O and substoichiometric nichrome oxide Ni-Cr-O respectively. Based on the totality of all the above requirements for the material of the outer "PRT" -layer of the thin-film optical energy-saving coating of the product, zinc-doped tin oxide Zn-Sn-O was chosen as the material of the outer layer, as the only material that simultaneously meets all the presented requirements.

The choice of the thickness of the intermediate layer containing substoichiometric aluminum nitride Al-N, ranging from 57 nm to 68 nm, is determined by two main conditions: the thickness of this layer must, on the one hand, be not less than a multiple of a quarter of the wavelength falling in the middle of the peak zone the infrared part of the solar radiation spectrum, so that it is possible to ensure the effect of interference attenuation during re-radiation between the layers of silver Ag that reflect infrared radiation, which are separated by an intermediate layer of zinc-doped tin oxide, which leads to a sharp decrease in the transmission of electromagnetic radiation by the product during the transition from visible to near-IR - the area of the solar radiation spectrum and, as a result, a decrease in the direct transmittance of solar radiation T _sol to less than 32% with a concomitant increase in the product selectivity coefficient S to a value of at least 1.384 units. On the other hand, the thickness of the intermediate layer should be no more than half of a multiple of at least one of the radiation wavelengths of the visible spectrum range corresponding to the color perception of human vision, characterized by the green / red color differentiation axis a * of the quasi-coordinate grid of the international standard CEILAB ( D65 / 10 °) with a value ranging from -5 to -0.5 relative units to ensure a silvery reflection of the glass substrate surface on the side opposite to the side on which the thin-film energy-efficient optical coating is applied, due to the absence of a contribution to the resulting position by the color quasi-coordinates of the red component, due to which the final color will be perceived to be shifted to the violet part of the visible spectrum along the UV border. Based on these two conflicting requirements, the range of acceptable values of the thickness of the intermediate layer containing substoichiometric aluminum nitride Al-N was determined, ranging from 57 nm to 68 nm.

In turn, the choice of the thickness of the first layer adjacent to the substrate surface containing a substoichiometric nitride of silicon doped with aluminum Si-Al-N, ranging from 17 nm to 21 nm, is also determined by two main conditions: on the one hand, the thickness of this layer should not be less than the maximum permissible the boundary value, starting from which the "antireflection effect" is observed, provided by the layer material, expressed in a degree sufficient to provide the entire set of layers with the corresponding thicknesses of a thin-film heat-resistant highly selective energy-saving coating on a glass substrate with a level of translucency, characterized by a transmittance of visible radiation T _{vis of} at least 42 %. On the other hand, the thickness of the first layer adjacent to the substrate surface containing a substoichiometric nitride of aluminum-doped silicon Si-Al-N should also not exceed the maximum permissible value along the upper boundary, starting from which the concentration of internal stresses from defects in the polycrystalline lattice of the finely dispersed structure of the layer material, including those induced during the heat treatment of the product with a relatively rapid heating of the substrate and its subsequent sharp cooling, will prevail over the SPT qualities of the layer, which will lead to cracking of the layers reflecting infrared radiation containing silver Ag, and, in the general case, subsequent mechanical degradation and subsequent partial or complete delamination of the entire set of thin-film layers of the heat-resistant highly selective energy-saving coating from the surface of the glass substrate. Based on these two conflicting requirements, the range of permissible values of the thickness of the first layer adjacent to the substrate surface containing substoichiometric aluminum-doped silicon nitride Si-Al-N was determined, ranging from 17 nm to 21 nm.

In this case, the ratio of the thickness of the layer containing substoichiometric aluminum-doped silicon nitride Si-Al-N to the total thickness of the second covering layer containing substoichiometric aluminum nitride Al-N and the outer layer containing zinc-doped tin oxide Zn-Sn-O should be in the range from 0.3 to 0.7. As it was experimentally found, when the ratio of the thicknesses of these layers is less than 0.3 (with the thickness of the first layer adjacent to the surface of the substrate containing substoichiometric nitride of silicon doped with aluminum Si-Al-N, corresponding to the range, the boundaries of which and the reasons for their choice are indicated above) the total thickness of the outer layer containing zinc-doped tin oxide Zn-Sn-O and of the second covering layer containing substoichiometric aluminum nitride Al-N reaches the maximum permissible value, at which violations of the “bleaching effect” of the layer of substoichiometric silicon nitride Si doped with aluminum begin to be observed -Al-N due to "parasitic" interference attenuation of radiation of wavelengths of the corresponding range when they pass the materials of the second covering and external "PRT" - layers containing substoichiometric aluminum nitride Al-N, and zinc-doped tin oxide Zn-Sn-O, respectively, the cumulative thickness is too large. At the same time, it was experimentally found that at the ratio of the thickness of the layer containing substoichiometric aluminum-doped silicon nitride Si-Al-N to the total thickness of the second covering layer containing substoichiometric aluminum nitride Al-N and the outer layer containing zinc-doped tin oxide Zn -Sn-O exceeding 0.7 (with the thickness of the first layer adjacent to the substrate surface containing substoichiometric nitride of aluminum-doped silicon Si-Al-N, corresponding to the range, the boundaries of which and the reasons for their choice are indicated above), the total thickness of the outer layer containing zinc-doped tin oxide Zn-Sn-O, and the second covering layer containing substoichiometric aluminum nitride Al-N, becomes too small to provide the entire complex of required qualities expected from a given pair of layers as part of the layer structure of the product: reliable chemomechanical protection in relation to the second reflective infrared radiation e layer of silver Ag, sufficient barrier properties in relation to an aggressive acidic environment and the process of diffusion of oxygen and reaction radicals from the external environment during the process of heat treatment of the product, as well as "PRT" - the quality of protection of the entire thin-film layer structure of a heat-resistant highly selective energy-saving coating on a glass substrate ...

The total thickness of two layers of a thin-film heat-resistant highly selective energy-saving coating of an article containing silver Ag, reflecting infrared radiation, is adjusted so that the surface ohmic resistance of the article does not exceed 2.19 Ohm / square, and only in this case is the total balance between the emissivity of the article realized, with the emissivity E not exceeding 2.4%, and the value of the transmittance of electromagnetic radiation in the visible wavelength range T _vis , which is not less than 42%, as a result of which the product has the qualities of high selectivity, expressed in achieving the selectivity coefficient S of not less than 1.384. In this case, the ratio of the thickness of the first layer reflecting IR radiation containing silver Ag to the thickness of the second layer reflecting IR radiation containing silver Ag should be in the range from 0.21 to 0.38. The lower of these limits is due to the fact that, as it was experimentally shown, only when the ratio between the thickness of the first layer reflecting IR radiation, containing silver Ag, and the thickness of the second layer reflecting IR radiation, containing silver Ag, is more than 0.21 antiphase resonance attenuation at wavelengths near ultraviolet will not affect the hue of the reflection of the product from the side of the surface of the glass substrate opposite to the side on which the thin-film energy-efficient optical coating is applied, along the a * color differentiation green / red axis of the quasi-coordinate grid of the international standard CEILAB (D65 / 10 °) in the direction of large values corresponding to the red shades of human color perception, while maintaining the possibility of achieving the position along the a * axis of colorimetric quasi-coordinates corresponding to values not exceeding -0.5 relative units, which is consistent with the technical result of the present invention enia. At the same time, the ratio of the thickness of the first layer reflecting IR radiation containing silver Ag to the thickness of the second layer reflecting IR radiation containing silver Ag should not exceed 0.38 so that the interference resonance peak falling on the visible part of the electromagnetic spectrum radiation, when re-emitted between the silver layers of a highly selective product platform with two layers reflecting infrared radiation, was observed at a wavelength of no more than half the value, a multiple of at least one of the wavelengths of radiation in the visible spectrum range corresponding to the color perception of human vision, characterized by the color b * axis differentiation of the yellow / blue quasi-coordinate grid of the international standard CEILAB (D65 / 10 °) with a value ranging from -5.2 to +2.5 relative units, to ensure a rich silver color of reflection of the glass substrate surface from the side opposite to the side on which applied thin-film energy efficiency optical coating in the entire range of viewing angles relative to the normal to the substrate surface.

In this case, the ratio of the thickness of the first barrier layer, which contains the substoichiometric oxide of nichrome Ni-Cr-O, to the total thickness of the first contact layer containing oxide doped with tin zinc Zn-Sn-O, and the first catalytic layer containing oxide doped with aluminum zinc Zn-Al -O, and the ratio of the thickness of the second barrier layer, which contains the substoichiometric oxide of nichrome Ni-Cr-O, to the total thickness of the second contact layer containing tin-doped zinc oxide Zn-Sn-O, and the second catalytic layer containing aluminum-doped zinc oxide Zn -Al-O, should be at least 0.19 so that the parasitic additional residual re-radiation between these two functional groups of layers of the highly selective platform of the product with two reflective thin-film layers of IR radiation does not have a shifting effect on the balance of the position according to the color coordinates of the quasi-coordinate grid of the international CEILAB standard (D65 / 10 °) a * and b * achievable by adjusting the ratio of the thicknesses of the IR-reflecting thin-film coating layers containing silver Ag and the thickness of the intermediate layer containing substoichiometric aluminum nitride Al-N within the limits indicated and explained above, which ensures the bronze color of the reflection of the glass substrate surface from the side opposite to the side, on which a thin-film energy-efficient optical coating is applied. In addition, it has been empirically found that the ratio of the thickness of the first barrier layer, which contains the substoichiometric oxide of nichrome Ni-Cr-O, to the total thickness of the first contact layer containing tin-doped zinc oxide Zn-Sn-O, and the first catalytic layer containing the oxide aluminum-doped zinc Zn-Al-O, and the thickness of the second barrier layer, which contains substoichiometric nichrome oxide Ni-Cr-O, to the total thickness of the second contact layer containing tin-doped zinc oxide Zn-Sn-O, and the second catalytic layer containing aluminum-doped zinc oxide Zn-Al-O, on the other hand, should also not, on the other hand, exceed the value of 0.52, in order to also exclude the influence of parasitic additional residual re-radiation between these two functional groups of layers of a highly selective product platform with two reflective infrared radiation thin-film layers on the effect of spectral broadening from an intermediate layer containing a substoichiometer chemical aluminum nitride Al-N.

At the same time, the ratio of the thickness of the second barrier layer, which contains the substoichiometric oxide of nichrome Ni-Cr-O, to the thickness of the first barrier layer, containing the substoichiometric oxide of nichrome Ni-Cr-O, should be in the range from 0.4 to 11.6. The lower limit of this range is associated with the fact that when the ratio of the thickness of the second barrier layer, which contains the substoichiometric oxide of nichrome Ni-Cr-O, to the thickness of the first barrier layer, containing the substoichiometric oxide of nichrome Ni-Cr-O, is less than 0.4, excessive resonance effects on the transmission spectrum of electromagnetic radiation in the near infrared wavelength range of the order of 900-1200 nm and the visible wavelength range of the order of 400-750 nm, which, in turn, will lead to a decrease in the selectivity coefficient S of the final product through an increase in the direct transmission coefficient infrared component of solar radiation T _IR due to the inverse compensation of interference processes occurring during the successive overcoming of two nanosized layers of silver Ag by radiation falling on the coating, along with a simultaneous decrease in the light transmission of the entire aggregate thin-film layer structure of the described product in the visible wavelength range T _{v is} due to the concomitant increase in the contribution of parasitic absorption in this range from the side of the barrier layers containing substoichiometric nichrome oxide Ni-Cr-O. At the same time, the upper limit of the range of the permissible ratio of the thickness of the second barrier layer, which contains the substoichiometric oxide of nichrome Ni-Cr-O, to the thickness of the first barrier layer, which contains the substoichiometric oxide of nichrome Ni-Cr-O, equal to 11.6, was selected on the basis of that, as it was empirically determined, at a ratio exceeding this value, the thickness of the second barrier layer containing substoichiometric oxide of nichrome Ni-Cr-O becomes so large that this leads to the induction of parasitic stresses at the boundary of this layer and the layer immediately below it with respect to glass substrate of the article of the second infrared reflecting layer, which contains silver Ag. Due to this, degradation of the adhesion properties occurs between the corresponding layers - namely, the second reflective IR-radiation layer containing silver Ag, and the second barrier layer containing substoichiometric oxide of nichrome Ni-Cr-O - as a result of which the level of general mechanical stability of the entire layer structure deteriorates thin-film coating of the described product in relation to external influences. The latter also leads, in particular, to an increased probability of defoliation of the layer structure of the thin-film coating of the described product at the interface between the second reflecting IR-radiation layer containing silver Ag and the second barrier layer containing substoichiometric nichrome oxide Ni-Cr-O during thermal exposure. on the product, which affects the deterioration of the thermal stability of the energy-saving coating on the glass substrate, declared as one of the technical results of the present invention.

The need to maintain the ratio of the thickness of the first contact layer containing tin-doped zinc oxide Zn-Sn-O to the thickness of the first catalytic layer containing aluminum-doped zinc oxide Zn-Al-O, as well as the thickness of the second contact layer containing tin-doped zinc oxide Zn- Sn-O, to the thickness of the second catalytic layer containing oxide doped with aluminum zinc Zn-Al-O, in the range from 0.18 to 15.65 is associated with a combination of the following reasons. If the ratio of the thicknesses of individual layers in these two functional groups — the sequence of the contact and catalytic layers — exceeds 15.65, the thickness of the contact layer will obviously significantly prevail over the thickness of the catalytic layer. As it was empirically revealed, for the case of using these materials of the described functional layers - namely, tin-doped zinc oxide Zn-Sn-O as the material of the first and second contact layers of the thin-film coating and oxide doped with aluminum zinc Zn-Al-O as the material of the first and the second catalytic layers of a thin-film coating - when the specified upper limit of the permissible ratio of layer thicknesses is exceeded, recrystallization processes in an excess in its thickness, in comparison with the catalytic layer, the contact layer will affect the effect of translation of the changed crystal structure by the catalytic oxide layer lying above the glass substrate of the product doped with aluminum zinc Zn-Al-O. The latter will, in turn, lead to the loss of its direct catalytic properties of ensuring uniform growth of the silver Ag layer, which is deposited on top of it with respect to the glass substrate of the product, through the subsequent broadcasting of the features of the structure of the contact layer subjected to recrystallization effects, containing oxide doped with tin zinc Zn-Sn -O. Along with this, at the ratio of the thickness of the first contact layer containing oxide doped with tin zinc Zn-Sn-O to the thickness of the first catalytic layer containing oxide doped with aluminum zinc Zn-Al-O, as well as the thickness of the second contact layer containing oxide doped with tin zinc Zn-Sn-O, to the thickness of the second catalytic layer containing oxide doped with aluminum zinc Zn-Al-O, less than the value of the lower permissible limit of 0.18, the thickness of the catalytic layer will obviously significantly prevail over the thickness of the underlying relative glass the substrate of the product of the contact layer, which will negatively affect the adhesion properties of the contact layer containing zinc oxide doped with tin Zn-Sn-O, due to the induction of parasitic stresses into the layer, associated mainly with interstitial defects, from the side of a thick layer of oxide doped with aluminum zinc Zn-Al-O, which is a catalytic layer. As a result, as it was revealed in the course of empirical studies, the intersection of the lower limit of the permissible range of the thickness ratios of the described layers, which is 0.18, leads to the registration of degradation of the layer structure of the product during heat treatment, expressed in defoliation of the product having a reduced, due to the redistribution of the above-noted induced in parasitic stresses from the side of the thick catalytic layer, adhesion of the Zn-Sn-O contact layer, followed by delamination of the entire thin-film structure deposited on top of it. As a result, based on the requirements arising from the above observations, the boundaries of the permissible range of the ratio of the thickness of the first contact layer containing tin-doped zinc oxide Zn-Sn-O to the thickness of the first catalytic layer containing aluminum-doped zinc oxide Zn-Al-O were determined, as well as the thickness of the second contact layer containing tin-doped zinc oxide Zn-Sn-O to the thickness of the second catalytic layer containing aluminum-doped zinc oxide Zn-Al-O, lying in the range from 0.18 at the lower boundary to 15.65 along the upper border.

At the same time, the thickness of the absorbing layer, which contains the substoichiometric tungsten nitride WN, should be such that the resulting direct transmission of electromagnetic radiation in the 385-790 THz range of the heat-resistant highly selective energy-saving silver-colored coating on glass is from 0.43 to 0.55. If the thickness of the absorbing layer containing substoichiometric tungsten nitride WN is excessively large, and, therefore, the contribution to the absorption intensity introduced by this layer to the total absorption spectrum of the described product is large, as a result of which the value of the direct transmission of electromagnetic radiation by the product in the range 385-790 THz will be less than 0.43, the antireflection qualities of the first and second contact layers containing tin-doped zinc oxide Zn-Sn-O, which these layers provide for the thin-film coating of the described product, will be insufficient to effectively minimize the distortion of the split beam when passing through the barrier layer metal for the purpose of the desired increase in the transparency of the product in relation to the wavelengths of the visible part of the solar spectrum of electromagnetic radiation at the level necessary to maintain the value of the integral light transmission of visible radiation T declared in the technical problem of the present invention _vis within not less than 42%. On the other hand, if the thickness of the absorbing layer containing substoichiometric tungsten nitride WN is, on the contrary, excessively small, and, accordingly, due to the low level of absorption intensity introduced by this layer into the total absorption spectrum of the described product, the value of the direct transmission of the product of electromagnetic radiation in the range 385 -790 THz will exceed 0.55. As a result, the effect of suppressing the growth of the transmission value with respect to the visible wavelength range of electromagnetic radiation and the accompanying shift of the position along the color quasi-coordinates a * / b * of the CEILAB standard (D65 / 10 °) provided by the absorbing layer of the substoichiometric tungsten nitride WN during thermal action on the thin film the layer structure of the coating of the article during heat treatment will be insufficient to suppress the shift in the balance of light transmission / absorption of the layer structure of the coating as a result of heat treatment in a range that makes it possible to achieve the desired saturated silver hue of light reflection from the side opposite to the side on which the thin-film energy-efficient optical coating is applied, in a wide range of angles observation, as well as for adjusting the value of the displacement of the position according to the color quasi-coordinates a * / b * of the CEILAB standard (D65 / 10 °) of the colorimetry of the light reflection of the product during heat treatment less than 3 units for each of and individual coordinates of the colorimetric quasispace. The latter leads to the loss of the possibility of providing the necessary saturated silvery shade of the product in the case of light reflection from the surface of the glass substrate from the side opposite to the side on which the thin-film energy-efficient optical coating is applied, achieved in a wide range of viewing angles and characterized by the following parameters of the reflection shade in color quasi-coordinates a * / b * of the international standard CEILAB (D65 / 10 °): a * from -5 to -0.5, and b * from -5.2 to +2.5, according to the declared technical problem of the present invention. Based on the above conflicting requirements, it was found that the thickness of the absorbing layer, which contains substoichiometric tungsten nitride WN, should be maintained at a level aligned with the thicknesses of the other layers of the described heat-resistant energy-efficient coating, selected according to the other stated requirements for the product, so that the resulting direct the transmission of electromagnetic radiation in the range of 385-790 THz of the heat-resistant highly selective energy-saving silver coating on the glass will be strictly within the range from 0.43 to 0.55.

The limit along the lower boundary of the permissible ratio of the thickness of the outer "PRT" -layer containing zinc-doped tin oxide Zn-Sn-O to the thickness of the first covering layer containing aluminum-doped zinc oxide Zn-Al-O, which is not less than 1.4, is connected with the fact that at values of the specified ratio below this limit, the effects of parasitic re-radiation between the group of layers consisting of the first covering layer containing the oxide doped with aluminum zinc Zn-Al-O and the first barrier layer containing the substoichiometric oxide of nichrome Ni-Cr-O, as well as an external "PRT" -layer containing zinc-doped tin oxide Zn-Sn-O, will lead to undesirable compensation for the inherent external "PRT" -layer containing zinc-doped tin oxide Zn-Sn-O, the effects of the absence of minimization of antireflection qualities manifested by the first layer adjacent to the surface of the glass substrate of the product and containing the substoichiometric nitride of silicon doped with aluminum Si-Al-N, due to the o that the absorption of light in a thin-film layer of Si-Al-N is very small in comparison with semitransparent layers of the subsequent deposited thin-film metal, during the passage of electromagnetic radiation of the visible wavelength range through the entire thickness of the thin-film layer structure of a heat-resistant highly selective energy-efficient coating of an article deposited on an optically transparent glass substrate; as a result of which the resulting balance between the coefficients of transparency and heat reflection of the product will be insufficient to provide the product with the final highly selective qualities, characterized, according to the technical problem of the present invention, with a selectivity S of at least 1.384.

In this case, the thickness of the outer "SPT" -layer containing zinc-doped tin oxide Zn-Sn-O should be at least 4 nm because thinner layers of zinc-doped tin Zn-Sn-O oxide exhibit so-called. the effects of "extinction", in which there is a local aggregation of layer components into submicron and micron globular crystalline formations over the underlying one, containing substoichiometric aluminum nitride Al-N and which is the second covering, as well as protective - to provide chemomechanical protection of the entire previously listed structure of the layers - the layer ... These aggregation effects, in addition, manifest themselves more intensively in the course of an energy-beneficial process, which is the process of heat treatment of the product, which introduces into the external "PRT" - a layer of zinc-doped tin Zn-Sn-O oxide, excess thermal energy during heating. As a result of the occurrence of "extinction" processes in the "PRT" -layer, its structural integrity, as well as the associated uniformity along the surface of the glass substrate of the product with a thin-film structure deposited on top of it, preceding the outer "PRT" -layer containing zinc-doped tin oxide Zn-Sn- O, the layers are violated, which leads to the fact that the layer ceases to exhibit the required "PRT" -quality, and, as a consequence, further propagation of cracks in the layer structure of the product during the initial concentration and subsequent relaxation of stresses at the boundaries of individual layers of individual materials during the processes temperature treatment associated with a sharp change in the substrate temperature, for example, during thermal quenching, which consists in rapid heating and subsequent sharp cooling of the product, leads to mechanical degradation of the thin-film structure of the described heat-resistant highly selective energy-efficient coating, up to its partial localized or noisy delamination from the surface of an optically transparent glass substrate. As a result, it was found that in order to prevent the above-described negative effects of heat treatment of the described article, the thickness of the outer "SPT" layer containing zinc-doped tin oxide Zn-Sn-O should be at least 4 nm.

In addition, the combined thickness of the second covering layer, which contains the substoichiometric aluminum nitride Al-N, and the outer "SPT" -layer containing zinc-doped tin oxide Zn-Sn-O, must be at least 24 nm. This is due to the fact that these two layers external with respect to the optically transparent glass substrate of the article are characterized by the most intense diffusion through them of highly mobile oxygen components with high kinetic energy from the atmosphere during heat treatment processes. As a result, to ensure an optimally high level of inhibition of oxygen supply during heat treatment deep into the part of the layer structure previously deposited with respect to the glass substrate due to the barrier of oxygen diffusion flow in the direction of the conductive metal layers, the diffusion distance of radicals through the thickness of these materials must exceed a certain thickness limit ensuring a sufficient loss of excess kinetic energy, and, as a consequence, the loss of initial mobility by radicals. This limit was found to be 24 nm for the case of the covering layer used for the above reasons, which contains substoichiometric aluminum nitride Al-N, and the outer "PRT" -layer containing zinc-doped tin oxide Zn-Sn-O, as well as applications exposure to temperature over 780 ° C for more than 15 minutes, which meets the technical problem of the present invention.

In this case, in a particular case, it is proposed to join a glass substrate with a multilayer heat-resistant highly selective energy-saving coating applied on its surface, previously subjected to a thermal hardening process, with at least one additional transparent substrate facing the outer layer of the coating containing zinc-doped tin oxide Zn- Sn-O. This solution makes it possible to further increase the chemomechanical stability of the product as a whole, since the entire structure of thin-film layers of an optical thermally stable highly selective energy-saving coating on the primary glass substrate is, in this case, protected from negative external influences and contact with the external environment by the thickness of the additional transparent substrate or the thickness of the first from a group of additional transparent substrates in direct contact with the outer surface of the outer thin-film layer containing zinc-doped tin oxide Zn-Sn-O, which is external relative to the primary glass substrate. This preserves the color of the reflection of the surface of the glass substrate on the side opposite to the side on which the thin-film energy-efficient optical coating is applied. In turn, preliminary thermal hardening of a glass substrate with a multilayer heat-resistant highly selective energy-saving coating applied to its surface provides additional impact resistance of the final product along with additional qualities of predominantly small-sized fragmentation of the heat-treated substrate in the event of initiation of an avalanche-like release of longitudinally oriented stresses from it, due to which an additional effect is provided to reduce the likelihood of getting cut wounds when the final product is broken.

At the same time, in another particular case, it is proposed to join a glass substrate with a multilayer heat-resistant highly selective energy-saving coating deposited on its surface, previously subjected to a thermal hardening process, with at least one additional transparent substrate facing the outer layer of the coating containing zinc-doped tin oxide Zn- Sn-O. This solution makes it possible to further increase the chemomechanical stability of the product as a whole, since the entire structure of thin-film layers of an optical thermally stable highly selective energy-saving coating on the primary glass substrate is, in this case, protected from negative external influences and contact with the external environment by the thickness of the additional transparent substrate or the thickness of the first from a group of additional transparent substrates in direct contact with the outer surface of the outer thin-film layer containing zinc-doped tin oxide Zn-Sn-O, which is external relative to the primary glass substrate. This preserves the color of the reflection of the surface of the glass substrate on the side opposite to the side on which the thin-film energy-efficient optical coating is applied. In turn, preliminary thermal hardening of a glass substrate with a multilayer heat-resistant highly selective energy-saving coating applied to its surface provides additional impact resistance of the final product along with additional qualities of resistance to spontaneous fragmentation of a heat-strengthened substrate in the event of initiation of an avalanche-like escape of longitudinally oriented stresses from it due to external temperature drop.

The implementation of the technical problem of the present invention is provided by means of a method for obtaining the described highly selective energy-saving silver-colored coating on glass during sequential sputtering of materials of sputtering cathode targets in the magnetron discharge plasma as described above. Due to the implementation of this method of deposition of a multilayer thin-film coating of an article, it is possible to maintain the parameters of the spraying process within the adjustment limits, which provide the required resulting performance characteristics of the obtained heat-resistant highly selective energy-saving coating on glass within the ranges given below in accordance with the technical problem of the present invention.

The deposition of the first layer adjacent to the surface of the glass substrate and containing substoichiometric nitride of aluminum-doped silicon Si-Al-N is carried out by sputtering a bi-metallic alloy SiAl doped with aluminum in the magnetron discharge plasma. Sputtering an all-metal target in the presence of the reaction component of the working gas mixture, which is nitrogen, and which is poured into the working volume of the spray chamber while maintaining the level of the gas injection flow in accordance with the requirements below, makes it possible to obtain the required substoichiometric state of the deposited layer, characterized by undersaturation with the nitrogen component. In this case, the degree of doping of the bi-metallic alloy of aluminum-doped silicon SiAl of the sputtered target should be from 2% to 60%. When the degree of doping is less than 2%, the concentration of the aluminum component in the deposited layer will be insufficient to effectively promote the additional formation of the most stable bonds with the subsequent deposited first contact layer containing tin-doped zinc oxide Zn-Sn-O. The resulting decrease in the level of adhesion at the boundary of individual layers of a thin-film coating of an article will ultimately lead to a violation of its structural integrity and mechanical resistance to external influences during operation, and, above all, heat treatment. On the other hand, the use of sputtering targets made of a bi-metallic alloy doped with aluminum silicon SiAl with a doping level higher than 60% will lead to an increased concentration of the aluminum component in the flow of the material sputtered from the target, and, as a result, in the composition of the deposited layer. will, in turn, facilitate the formation of monometallic aluminum phase precipitates in the coating layer. As a result of the latter, a fundamental uncompensated local decrease in the level of adhesion of the deposited layer to the surface of the glass substrate is observed due to a statistical decrease in the number of acts of “crosslinking” of the layer regions with crystalline precipitates of short-range order of the quasi-amorphous structure of the glass mass through free chemical bonds of silicon atoms with the formation of mainly covalent polar bonds. Thus, according to the combination of the above reasons, the deposition of the first layer adjacent to the surface of the glass substrate and containing substoichiometric nitride of aluminum-doped silicon Si-Al-N is required to be carried out by sputtering in the magnetron discharge plasma of a bi-metal alloy of aluminum-doped silicon SiAl with a doping level of from 2% to 60%.

In this case, the deposition of the subsequent layer, which is the first contact layer and containing oxide doped with tin zinc Zn-Sn-O, should be carried out by sputtering a metal sputtering target from a bi-metallic alloy doped with tin zinc ZnSn in the magnetron discharge plasma. Sputtering an all-metal target in the presence of the reaction component of the working gas mixture, which is oxygen, and which is poured into the working volume of the spray chamber while maintaining the level of the gas injection flow in accordance with the requirements below, makes it possible to minimize the thickness of the oxidized target layer, which is concentrated near its surface due to establishing a dynamic equilibrium between the rate of sputtering of the target surface and the dynamics of its oxidation, as well as the absorption of oxygen by the thickness of the bimetallic alloy. Due to this, in turn, it is possible to maintain the sputtering process in the modes of balance of the current-voltage characteristics of the magnetron discharge, which help to minimize the effect of disruption of the discharge into the arc mode, in which it occurs as damage to the surface of the sputtered target, which can lead to further unevenness of the thickness obtained in during the deposition of the layer over the surface area of the glass substrate, and the induction of additional parasitic tensile stresses in the forming thin film, which affects the degradation of the required contact properties of the layer. In this case, the degree of doping of the bi-metallic alloy doped with tin zinc ZnSn of the sputtered target should be from 5% to 80%. When using sputtered bi-metallic targets with doping levels outside the above limits, the difference between the concentrations of the main and alloying metal components of the deposited layer will be large enough to facilitate the processes of recrystallization of a thin film during the formation of an excessively large amount of monometallic phase precipitates of the prevailing metal concentration. Components. The changed morphology of the surface of the layer of the described coating subjected to recrystallization processes will be translated into subsequent deposited individual layers of the thin-film structure of the product, including into all-metal functional layers of silver Ag reflecting IR radiation, as a result of which an increase in the value of the turbidity of the glass substrate with the applied on it with an energy-efficient coating to values exceeding the value of 9.8-10 ^-2 % declared according to the technical result of the present invention, and the value of the turbidity of the product will further increase to large values during the heat treatment of the product due to further aggregation effects of functional reflective IR radiation of layers of silver Ag, subjected to the initial translation of the recrystallized structure of the underlying layers during the direct formation. As a result, for the above reasons, the deposition of the first contact layer containing tin-doped zinc oxide Zn-Sn-O should be carried out by sputtering in the magnetron discharge plasma of a metal sputtering target made of a bi-metallic alloy of tin-doped zinc ZnSn with a doping level of 5% or more up to 80%.

The deposition of the next layer, which is the first catalytic layer and containing oxide doped with aluminum zinc Zn-Al-O, should be carried out by sputtering in the magnetron discharge plasma of a metal sputtering target made of a bi-metal alloy doped with aluminum zinc ZnAl. Sputtering an all-metal target in the presence of the reaction component of the working gas mixture, which is oxygen, and which is poured into the working volume of the spray chamber while maintaining the level of the gas injection flow in accordance with the requirements below, makes it possible to minimize the thickness of the oxidized target layer, which is concentrated near its surface due to establishing a dynamic equilibrium between the rate of sputtering of the target surface and the dynamics of its oxidation, as well as the absorption of oxygen by the thickness of the bimetallic alloy. Due to this, in turn, it is possible to maintain the sputtering process in the modes of balance of the current-voltage characteristics of the magnetron discharge, which help to minimize the effect of disruption of the discharge into the arc mode, in which it occurs as damage to the surface of the sputtered target, which can lead to further unevenness of the thickness obtained in during the deposition of the layer over the surface area of the glass substrate, and the induction of additional parasitic tensile stresses in the forming thin film, which affects the degradation of the required contact properties of the layer. In this case, the degree of doping of the bi-metallic alloy doped with aluminum zinc ZnAl of the sputtered target should be from 5% to 80% for reasons similar to those for the material of the sputtered target, from which the first contact layer is deposited and which consists of a bimetallic alloy doped with tin zinc ZnSn, above. When sputtered bi-metallic targets of an aluminum-doped zinc alloy ZnAl with doping levels outside the range from 5% to 80%, the difference between the concentrations of the main and alloying metal components of the deposited layer will be large enough to facilitate the processes of recrystallization of a thin film during the formation a large number of monometallic phase precipitates of the prevailing concentration of the metal component. The changed morphology of the surface of the layer of the described coating subjected to recrystallization processes will be translated into subsequent deposited individual layers of the thin-film structure of the product, including into all-metal functional layers of silver Ag reflecting IR radiation, as a result of which an increase in the value of the turbidity of the glass substrate with the applied on it with an energy-efficient coating to values exceeding the value of 9.8-10 ^-2 % declared according to the technical result of the present invention, and the value of the turbidity of the product will further increase to large values during the heat treatment of the product due to further aggregation effects of functional reflective IR radiation of layers of silver Ag, subjected to the initial translation of the recrystallized structure of the underlying layers during the direct formation. As a result, the deposition of the first catalytic layer containing oxide doped with aluminum zinc Zn-Al-O should be carried out by sputtering in the magnetron discharge plasma of a metal sputtering target made of bimetallic alloy doped with aluminum zinc ZnAl with a degree of doping from 5% to 80%.

The subsequent layer that reflects infrared radiation and contains silver Ag should be deposited by sputtering a metal target consisting of solid silver Ag with an impurity metal purity of at least 90%. At lower values of impurity purity, the concentration of impurity components sputtered together with silver in the deposited layer will exceed the empirically established boundary value, starting from which the presence of an excess amount of impurities in the layer begins to provoke extinction processes and concomitant aggregation of the noble metal layer during heat treatment, regardless of its a specific thickness in the range of values defined and justified above. As a result, the initiation of accompanying processes of recrystallization of a thin film will occur, both of the layer of silver Ag directly containing an excess amount of impurity components, and of other layers of the thin-film coating structure of the described product deposited on top of it during the translation of the morphology of the layer reflecting infrared radiation that underwent initial local aggregation, as a result what will be an increase in the value of the turbidity of the glass substrate coated with an energy-efficient coating to values exceeding the value declared according to the technical result of the present invention of 9.8-10 ^-2 %. Thus, the deposition of a thin-film silver Ag layer, which is the first layer that reflects IR radiation, should be carried out by sputtering a sputtering cathode target made of Ag silver with an impurity purity of at least 90% in the magnetron discharge plasma.

In this case, the deposition of the next layer, which is the first barrier layer containing the substoichiometric oxide of nichrome Ni-Cr-O, should be carried out in the course of sputtering a target made of a bi-metallic alloy of nichrome NiCr with a partial nickel concentration of at least 10%. Sputtering an all-metal alloy target in the presence of the reaction component of the working gas mixture, which is oxygen, and which is admitted into the working volume of the spray chamber while maintaining the level of the gas injection flow in accordance with the requirements below, makes it possible to minimize the thickness of the oxidized layer of the target, which is concentrated near its surface behind due to the establishment of a dynamic equilibrium between the rate of sputtering of the target surface and the dynamics of its oxidation, as well as the absorption of oxygen by the thickness of the bi-metallic alloy. Due to this, in turn, it is possible to maintain the sputtering process in the modes of balance of the current-voltage characteristics of the magnetron discharge, which help to minimize the effect of disruption of the discharge into the arc mode, in which it occurs as damage to the surface of the sputtered target, which can lead to further unevenness of the thickness obtained in during the deposition of the layer over the surface area of the glass substrate, and the induction of additional parasitic tensile stresses in the forming thin film, which affects the degradation of the required contact properties of the layer. In turn, the limitation on the partial concentration of nickel in the composition of the target alloy, which should be at least 10%, is due to the fact that at a lower concentration of nickel in the composition of the bi-metallic alloy of the target, its concentration in the composition of the deposited layer will also be less than the empirically established lower the boundary value, before reaching which nickel plays the role of a conditional precursor component in the deposited layer, ensuring the presence of a chemical potential gradient in the forming layer of a magnitude sufficient in magnitude to provoke the formation of diffusion flows, leading to a collective crystallization growth of mono-element phase precipitates in the layer. The changed morphology of the surface of the layer of the described coating subjected to the processes of collective crystallization will be translated into subsequent deposited individual layers of the thin-film structure of the product, including the second all-metal functional layer of silver Ag reflecting IR radiation, as a result of which an increase in the value of the turbidity of the glass substrate will be observed. with an energy-efficient coating applied to it to values exceeding the value of 9.8-10 ^-2 % declared according to the technical result of the present invention, and the value of the turbidity of the product will further increase to large values during the heat treatment of the product due to further aggregation effects of the second functional reflecting infrared radiation layer of silver Ag, which underwent the initial broadcast of the collectively crystallized structure of the underlying layers in the course of direct formation. Thus, the deposition of the first barrier layer containing the substoichiometric oxide of nichrome Ni-Cr-O should be carried out by sputtering in the magnetron discharge plasma of a metal sputtering target made of a bimetallic alloy of nichrome NiCr alloy with a partial nickel concentration of at least 10%.

The deposition of the subsequent layer of oxide doped with aluminum zinc Zn-Al-O, which plays the role of the first covering layer, should be carried out by sputtering in the plasma of a magnetron discharge of a dielectric target from a ceramic stoichiometric oxide of a bi-metallic alloy doped with aluminum zinc ZAO with a degree of alloying from 5% to 80% ... The use of a preoxidized ceramic target in this case is due to the fact that, when using it, the oxygen required for the formation of the oxide of the deposited layer enters the substrate as part of the flow of the sputtered substance from the target, incl. in the molecular form of oxides of the metal component of the deposited coating. Thus, the minimization of the negative impact of the highly reactive oxygen component on the previously deposited ones is ensured: the all-metal first functional layer reflecting IR radiation and consisting of silver Ag, followed by a substoichiometric layer of nichrome oxide Ni-Cr-O, which is the first barrier layer; which are exposed to the environment inside the sputtering chamber, in which the first covering layer of oxide doped with aluminum zinc Zn-Al-O is deposited, as well as to the magnetron plasma discharge and the flow of the substance sputtered from the cathode target in it. In the case of the deposition of the first covering layer, consisting of an oxide doped with aluminum zinc Zn-Al-O, by reaction sputtering of a metal target in the presence of oxygen admitted into the sputtering chamber as a reaction component of a mixture of working gases, arriving at the surface of previously deposited thin-film layers on a glass substrate high-energy oxygen ions undergoing ionization in the combustion region of a magnetron plasma discharge, as well as molecular oxygen chemisorbed into the outer layers, at the described stage of the formation of the structure of a thin-film energy-efficient coating of the product, layers of metallic silver Ag and substoichiometric oxide nichrome Ni-Cr-O, damage these layers through the formation of an excessive number of implantation defects beforehand, as a covering layer of zinc-doped zinc oxide Zn-Al-O thick enough to protect them, as a result of which this group of layers loses m the required level of adhesion at the interface boundaries of both the individual layers of the group and in relation to other layers of the thin-film structure of the coating as a whole, which leads to a significant degradation of the qualities of the mechanical stability of the coating of the described product and further impossibility of ensuring the combination of the product qualities declared in the technical result of the present invention. At the same time, the reasons why the degree of doping of the ceramic stoichiometric oxide of the bimetallic alloy doped with aluminum zinc ZAO, of which the sputtered cathode target used to deposit the first covering layer of the oxide doped with aluminum zinc Zn-Al-O, should be in the range from 5% to 80 % for reasons similar to those for a target made of a bi-metallic alloy of aluminum-doped zinc ZnAl, with which, as described above, the first catalytic layer containing aluminum-doped zinc oxide Zn-Al-O should be deposited: when using ceramic sputtered targets of stoichiometric oxide bi-metallic alloy alloyed with aluminum zinc ZAO with alloying degrees outside the range from 5% to 80%, the difference between the concentrations of the main and alloying metal components of the deposited layer will be large enough to promote the processes of recrystallization of a thin film during the formation of excess there is a large amount of monometallic phase precipitates of the prevailing concentration of the metal component. The changed morphology of the surface of the layer of the described coating subjected to recrystallization processes will be translated into subsequent individual layers of the thin-film structure of the product, which are deposited in the future, including the second all-metal functional layer of silver Ag reflecting IR radiation, as a result of which an increase in the value of the turbidity of the glass substrate with applied to it with an energy efficient coating to values exceeding the value of 9.8-10 ^-2 % declared according to the technical result of the present invention, and the value of the turbidity of the product will further increase to large values during the heat treatment of the product due to the further effects of aggregation of the second functional reflective IR radiation of a layer of silver Ag, which underwent the initial translation of the recrystallized structure of the underlying layers during direct formation. Thus, the deposition of the first covering layer containing zinc oxide doped with aluminum Zn-Al-O should be carried out by sputtering in the plasma of a magnetron discharge of a dielectric target made of ceramic stoichiometric oxide of a bi-metallic alloy doped with aluminum zinc ZAO with a doping level from 5% to 80% ...

In this case, the deposition of the next layer, which is an intermediate layer and contains substoichiometric aluminum nitride Al-N, is carried out by sputtering an all-metal aluminum target with an impurity purity of at least 84%. Sputtering an all-metal target in the presence of the reaction component of the working gas mixture, which is nitrogen, and which is admitted into the working volume of the spray chamber while maintaining the level of the gas injection flow in accordance with the requirements below, makes it possible to minimize the thickness of the nitrogen-poisoned layer of the target, which is concentrated near its surface due to the establishment of a dynamic equilibrium between the rate of sputtering of the target surface and the dynamics of its poisoning, as well as the absorption of nitrogen by the thickness of aluminum. Due to this, in turn, it is possible to maintain the sputtering process in the modes of balance of the current-voltage characteristics of the magnetron discharge, which help to minimize the effect of disruption of the discharge into the arc mode, in which it occurs as damage to the surface of the sputtered target, which can lead to further unevenness of the thickness obtained in during the deposition of the layer over the surface area of the glass substrate, and the induction of additional parasitic tensile stresses in the forming thin film, which affects the degradation of the required contact properties of the layer. In this case, the restriction on the minimum permissible purity of the target material is due to the fact that at lower values of the impurity purity, the concentration of impurity components sputtered together with aluminum in the deposited layer will exceed the empirically established boundary value, starting from which the presence of an excess amount of impurities in the layer begins to provoke recrystallization processes and the accompanying aggregation of the layer during heat treatment, regardless of its specific thickness, lying in the range of values determined and justified above. As a result, both the direct recrystallization of a thin film of the layer of substoichiometric aluminum nitride Al-N containing an excessive amount of impurity components, and other layers of the thin-film coating structure of the described product deposited on top of it, will occur during the translation of the morphology of the intermediate layer subjected to initial local aggregation, as a result of which there will be an increase in the haze value of the glass substrate coated with an energy efficient coating to values exceeding the value of 9.8-10-2% declared according to the technical result of the present invention. Thus, the deposition of an intermediate layer containing substoichiometric aluminum nitride Al-N should be carried out by sputtering a sputtering cathode target made of aluminum Al with an impurity purity of at least 84% in the magnetron discharge plasma.

Since in order to realize the qualities of high selectivity of the product, the layer structure of the thin-film coating of the product is performed according to the platform scheme with two layers included in the coating, reflecting IR radiation and containing silver, separated by ceramic layers, as well as the selected scheme for constructing a thin-film optical energy-saving coating of the product suggests, for the above reasons , repetition of the general structure of successively successive materials in the case of IR reflecting layers containing silver Ag and surrounding dielectric layers, namely: a second contact layer containing tin-doped zinc oxide Zn-Sn-O, a second catalytic layer, which contains oxide doped with aluminum zinc Zn-Al-O, directly the second reflecting IR-radiation layer containing silver Ag, and the second barrier layer containing substoichiometric nichrome oxide Ni-Cr-O, then for the deposition of the listed sequence of layers follows use appropriate sputtering targets similar to those for the layer group consisting of the first IR reflecting silver Ag layer and the surrounding dielectric layers - the first contact layer, the first catalytic layer, and the first barrier layer, respectively - for reasons similar to those described above. Thus, the deposition of the second contact layer containing tin-doped zinc oxide Zn-Sn-O should be carried out by sputtering in the magnetron discharge plasma of a metal sputtering target made of a tin-doped zinc ZnSn bi-metal alloy with a doping level of 5% to 80%, the deposition of the second catalytic layer containing aluminum-doped zinc oxide Zn-Al-O should be carried out by sputtering in the magnetron discharge plasma a metal sputtering target made of a bi-metallic alloy doped with aluminum zinc ZnAl with a doping degree of 5% to 80%, deposition of thin-film silver Ag the layer, which is the second layer reflecting infrared radiation, should be carried out by sputtering a sputtering cathode target made of silver Ag with an impurity purity of at least 90% in the magnetron discharge plasma, and the deposition of the second barrier layer containing substoichiometric nichrome oxide Ni-Cr-O should be spray I in the plasma of a magnetron discharge of a metal sputtering target made of a bi-metal alloy of an alloy of nichrome NiCr with a partial concentration of nickel not lower than 10%.

In this case, the deposition of a layer containing substoichiometric tungsten nitride WN and being an absorbing layer should be carried out by sputtering an all-metal tungsten W target with an impurity purity of at least 93% in the magnetron discharge plasma. Sputtering an all-metal target in the presence of the reaction component of the working gas mixture, which is nitrogen, and which is admitted into the working volume of the spray chamber while maintaining the level of the gas injection flow in accordance with the requirements below, makes it possible to minimize the thickness of the nitrogen-poisoned layer of the target, which is concentrated near its surface due to the establishment of a dynamic equilibrium between the rate of sputtering of the target surface and the dynamics of its poisoning, as well as the absorption of nitrogen by the tungsten mass W. This, in turn, makes it possible to maintain the sputtering process in the modes of balancing the current-voltage characteristics of the magnetron discharge, which help to minimize the effect of stripping burning of the discharge into the arc mode, in which it occurs as damage to the surface of the sputtered target, which can lead to further unevenness of the thickness of the layer obtained during deposition over the surface area of the glass substrate, and the induction of additional parasitic tensile stresses in the forming thin film, which affects the degradation of the required contact properties of the layer. In this case, the restriction on the minimum permissible purity of the target material is due to the fact that at lower values of impurity purity, the concentration of impurity components sputtered together with tungsten in the deposited layer will exceed the empirically established boundary value, starting from which the presence of an excess amount of impurities in the layer begins to provoke recrystallization processes and the accompanying aggregation of the layer during heat treatment, regardless of its specific thickness, lying in the range of values determined and justified above. As a result, both direct recrystallization of a thin film of the layer of substoichiometric tungsten nitride WN containing an excessive amount of impurity components, and other layers of the thin-film structure of the coating of the described article deposited on top of it will occur during the translation of the morphology of the absorbing layer subjected to initial local aggregation, as a result of which an increase in the value of the haze of a glass substrate with an energy-efficient coating applied to it to values exceeding the value declared according to the technical result of the present invention of 9.8-10 ^-2 %. Thus, the deposition of an absorbing layer containing substoichiometric tungsten nitride WN should be carried out by sputtering a sputtering cathode target made of tungsten W with an impurity purity of at least 93% in the magnetron discharge plasma.

The second covering layer following the absorbing layer of substoichiometric tungsten nitride WN, which also performs the function of a protective layer providing chemomechanical protection of the entire previously listed layer structure and containing substoichiometric aluminum nitride Al-N, is obtained by deposition during sputtering in a magnetron discharge plasma of an all-metal aluminum target with impurity purity of at least 84% for reasons similar to those for a layer of similar material - an intermediate layer containing substoichiometric aluminum nitride Al-N - and stated above. Namely: sputtering an all-metal target in the presence of the reaction component of the working gas mixture, which is nitrogen, and which is admitted into the working volume of the spray chamber while maintaining the level of the gas injection flow in accordance with the requirements below, makes it possible to minimize the thickness of the nitrogen-poisoned target layer, which is concentrated near its surface due to the establishment of a dynamic equilibrium between the rate of sputtering of the target surface and the dynamics of its poisoning, as well as the absorption of nitrogen by the thickness of aluminum. Due to this, in turn, it is possible to maintain the sputtering process in the modes of balance of the current-voltage characteristics of the magnetron discharge, which help to minimize the effect of disruption of the discharge into the arc mode, in which it occurs as damage to the surface of the sputtered target, which can lead to further unevenness of the thickness obtained in during the deposition of the layer over the surface area of the glass substrate, and the induction of additional parasitic tensile stresses in the forming thin film, which affects the degradation of the required contact properties of the layer. In this case, the restriction on the minimum permissible purity of the target material is due to the fact that at lower values of the impurity purity, the concentration of impurity components sputtered together with aluminum in the deposited layer will exceed the empirically established boundary value, starting from which the presence of an excess amount of impurities in the layer begins to provoke recrystallization processes and the accompanying aggregation of the layer during heat treatment, regardless of its specific thickness, lying in the range of values determined and justified above. As a result, both the direct recrystallization of a thin film of the layer of substoichiometric aluminum nitride Al-N containing an excessive amount of impurity components, and the subsequent layer deposited on top of it, which is the outer layer of the entire structure of the coating layers and plays the role of a "PRT" -layer, will occur. contains zinc-doped tin oxide Zn-Sn-O, during translation of the morphology of the second layer of substoichiometric aluminum nitride Al-N, which underwent initial local aggregation, which also acts as a protective layer to provide chemomechanical protection of the entire previously listed layer structure. As a result, both an increase in the haze value of a glass substrate with an energy-efficient coating applied to it to values exceeding the value of 9.8-10 ^-2 % declared according to the technical result of the present invention, and a loss of the "PRT" product external relative to the glass substrate, will be observed. a layer of zinc-doped tin oxide Zn-Sn-O of its qualities contributing to the prevention of crack propagation, which, in turn, will adversely affect the properties of the overall chemomechanical stability of the entire thin-film thermostable high-selective energy-saving silver-colored coating on the glass substrate as a whole. Thus, the deposition of the second covering layer containing the substoichiometric aluminum nitride Al-N should be carried out by sputtering in the magnetron discharge plasma of a sputtering cathode target made of aluminum Al with an impurity purity of at least 84%.

The outer layer of the entire structure of the coating layers, which plays the role of a "PRT" -layer and contains oxide doped with zinc tin Zn-Sn-O, is deposited by sputtering a cathode target from a bi-metallic alloy doped with tin zinc ZnSn with a doping level of 5% to 80 %. Sputtering an all-metal target in the presence of the reaction component of the working gas mixture, which is oxygen, and which is poured into the working volume of the spray chamber while maintaining the level of the gas injection flow in accordance with the requirements below, makes it possible to minimize the thickness of the oxidized target layer, which is concentrated near its surface due to establishing a dynamic equilibrium between the rate of sputtering of the target surface and the dynamics of its oxidation, as well as the absorption of oxygen by the thickness of the bimetallic alloy. Due to this, in turn, it is possible to maintain the sputtering process in the modes of balance of the current-voltage characteristics of the magnetron discharge, which help to minimize the effect of disruption of the discharge into the arc mode, in which it occurs as damage to the surface of the sputtered target, which can lead to further unevenness of the thickness obtained in during the deposition of the layer over the surface area of the glass substrate, and the induction of additional parasitic tensile stresses in the forming thin film, which affects the degradation of the required contact properties of the layer. In this case, the requirement that the degree of doping of the bi-metallic alloy of tin-doped zinc ZnSn of the sputtered target should be from 5% to 80% is due to the fact that when using sputtered bi-metallic targets with doping levels outside the above limits, the difference between the concentrations the main and alloying metal components of the deposited layer will be large enough to facilitate the processes of recrystallization of a thin film during the formation of an excessively large amount of monometallic phase precipitates of the metal component prevailing in its concentration. The occurrence of recrystallization processes in the layer of the described coating will lead to a concomitant accumulation of stresses at the boundaries of individual crystallites of the layer during their growth, which, in turn, will negatively affect the level of the "PRT" layer manifested by the layer and, as a result, degradation of the mechanical stability of the thin-film coating of the described product during heat treatment, as a set of processes that provoke the redistribution of internal stresses in the thickness of the layer structure being heated. As a result, for the above reasons, the deposition of a layer external with respect to the entire described thin-film layer structure of the coating, which acts as a "PRT" -layer and contains zinc-doped tin oxide Zn-Sn-O, should be carried out by sputtering in the magnetron discharge plasma with a metal sputtering targets made of bi-metallic alloy doped with tin zinc ZnSn with a doping level of 5% to 80%

In this case, the combustion voltage of a magnetron discharge during sputtering of cathode targets made of a bi-metallic alloy doped with aluminum silicon SiAl and aluminum Al should be maintained in the range from 420 to 560 V. This limitation on the range of permissible operating values of the combustion voltage of a magnetron discharge during sputtering of these cathode targets is related to with the fact that at voltage values less than 420 V, the kinetic energy of the sputtering plasma ions accelerated in the potential difference of the discharge gap of the magnetron unit will be insufficient to knock out aluminum atoms from the target surface with, in turn, a sufficiently high kinetic energy of leaving the near-surface potential barrier of the target, which, based on the results of overcoming the discharge gap and the flow of sputtered atoms onto the substrate, would allow them to ensure the formation of bonds with nearby atoms - both the forming layer and the underlying surface - necessary to achieve both satisfactory the visual adhesion of the deposited layers to the surface to be deposited, and the stability of the immediately forming thin-film layer in terms of the affinity of its individual monoatomic layers during formation. On the other hand, when the permissible limit value of the combustion voltage of a magnetron discharge is exceeded when cathode targets are sputtered from a bi-metallic alloy doped with aluminum silicon SiAl and from aluminum Al along the upper limit, which is 560 V, the dynamics of accumulation of a parasitic positive charge on the surface of the cathode targets of these materials, sprayed in states of surface poisoning, corresponding to the levels of flows of puffing of the reaction components of mixtures of working gases of the corresponding processes, which are within the limits, the boundaries and reasons for choosing which are given below, will be too high, which will begin to lead to systematic breakdowns of the combustion mode of the magnetron discharge into the state of an arc discharge, shadow the area of which will be initiated on the poisoned target surfaces. In this case, the disruption of the discharge burning to the arc mode will lead to damage to the surface of the sputtered target, which, in turn, leads to further unevenness of the thickness of the layer obtained during deposition over the surface area of the glass substrate, as well as to the induction of additional parasitic tensile stresses in the forming thin film, which affects the degradation of the required contact qualities of the deposited layer.

In this case, the combustion voltage of the magnetron discharge during sputtering of cathode targets made of a bi-metallic alloy doped with tin zinc ZnSn and from a bimetallic alloy doped with aluminum zinc ZnAl should be maintained in the range from 420 to 510 V. This restriction on the range of permissible operating voltage values of the of the indicated cathode targets is due to the fact that, as it was found, at voltage values less than 420 V, the kinetic energy of the sputtering plasma ions accelerated in the potential difference of the discharge gap of the magnetron unit of the magnetron unit will be insufficient to knock out zinc atoms from the target surface, as well as aluminum - for the case of targets from bimetallic alloy doped with aluminum zinc ZnAl - with, in turn, a sufficiently high kinetic energy of leaving the near-surface potential barrier of the target, which, according to the results of overcoming the discharge gap and the flow of sputtered atoms onto the substrate, n would allow them to ensure the formation of bonds with nearby atoms - both the forming layer and the underlying surface - necessary to achieve both satisfactory adhesion of the deposited layers to the deposited surface and the stability of the immediately forming thin-film layer in terms of the affinity of its individual monatomic layers during formation ... On the other hand, when the permissible limit value of the combustion voltage of a magnetron discharge is exceeded when cathode targets are sputtered from a bi-metallic alloy doped with tin zinc ZnSn and from a bi-metallic alloy doped with aluminum zinc ZnAl along the upper limit, which is 510 V, the dynamics of accumulation of a parasitic positive the surfaces of the cathode targets of the indicated materials, sputtered in states of surface poisoning, corresponding to the levels of flows of the puffing of the reaction components of mixtures of working gases of the corresponding processes, which are within the limits, the boundaries and reasons for choosing which are given below, will be too high, which will begin to lead to systematic breakdowns of the combustion mode of the magnetron discharge into the state of an arc discharge, the shadow region of which will be initiated on the poisoned surfaces of targets. In this case, the disruption of the discharge burning to the arc mode will lead to damage to the surface of the sputtered target, which, in turn, leads to further unevenness of the thickness of the layer obtained during deposition over the surface area of the glass substrate, as well as to the induction of additional parasitic tensile stresses in the forming thin film, which affects the degradation of the required contact qualities of the deposited layer.

Similar reasons impose restrictions on the empirically identified range of permissible values of the combustion voltages of a magnetron discharge, which should be maintained when sputtering cathode targets made of a bi-metallic alloy of nichrome NiCr and tungsten W, ranging from 550 to 610 V. This restriction on the range of permissible operating values of the combustion voltage magnetron discharge during the sputtering of these cathode targets is due to the fact that at voltage values less than 550 V, the kinetic energy of the sputtering plasma ions accelerated in the potential difference of the discharge gap of the magnetron unit of the magnetron unit will be insufficient to knock out nickel Ni atoms from the target surface from the bi-metallic alloy NiCr nichrome NiCr, and from the surface of tungsten targets, W atoms, respectively, of tungsten, with, in turn, a sufficiently high kinetic energy of leaving the near-surface potential barrier of the target, which, according to the results of overcoming the discharge gap and sputtered atoms onto the substrate, would allow them to ensure the formation of bonds with nearby atoms - both the forming layer and the underlying surface - necessary to achieve both satisfactory adhesion of the deposited layers to the surface being deposited and the stability of the immediately forming thin-film layer in terms of the affinity of its individual monatomic layers during formation. On the other hand, when the permissible limit value of the combustion voltage of a magnetron discharge is exceeded when cathode targets made of a bi-metallic alloy of nichrome NiCr and of tungsten W are sputtered along the upper limit, which is 610 V, the dynamics of accumulation of a parasitic positive charge on the surface of the cathode targets of these materials sputtered into states of surface poisoning, corresponding to the levels of flows of admission of reaction components of mixtures of working gases of the corresponding processes, which are within the limits and the reasons for choosing which are given below, will be, as it was revealed, too high, which will begin to lead to systematic breakdowns of the combustion mode of the magnetron discharge into the state of arc discharge, the shadow area of which will be initiated on the poisoned target surfaces. In this case, the disruption of the discharge burning to the arc mode will lead to damage to the surface of the sputtered target, which, in turn, leads to further unevenness of the thickness of the layer obtained during deposition over the surface area of the glass substrate, as well as to the induction of additional parasitic tensile stresses in the forming thin film, which affects the degradation of the required contact qualities of the deposited layer.

At the same time, when sputtering cathode targets made of silver Ag, the burning voltage of the magnetron discharge should not exceed 480 V. This is due to the fact that, as it was empirically established, when this limit is exceeded, the kinetic energy of individual silver atoms Ag arriving in the flow sputtered from the target substances on the surface of the exposed substrate with pre-applied layers of the described thin-film energy-efficient coating, in particular, the first and second catalytic layers preceding both the first and the second functional reflective IR-radiation layer of silver Ag, respectively, with the first and second catalytic layers containing aluminum-doped zinc oxide Zn-Al- O will be high enough to be damaged through induction of defects in the catalytic layers during the formation of primary monoatomic layers of silver Ag over the directly corresponding catalytic layers of aluminum doped zinc oxide Zn-Al-O. As a result, there will be a violation of the catalysis of the uniformity of growth of the electrically conductive metal layer of silver Ag, which is the first reflecting IR-radiation layer, over the catalytic layer containing the oxide of zinc doped with aluminum Zn-Al-O, both locally over the substrate surface and over the entire area. deposited layer structure, due to which the possibility of achieving energy efficiency qualities along the surface of the product in terms of reducing radiative heat losses in cold weather, corresponding to the value of the emissivity of the product specified by the surface ohmic resistance of the thin-film coating, not exceeding 2.19 Ohm / square, will also be locally disturbed, which will be the final consequence of the structural inhomogeneity of the electroconductive Ag layer reflecting IR radiation and the concomitant increase in parasitic resistance at the boundaries of the crystalline conglomerates of the thin-film silver layer.

In turn, when sputtering cathode targets made of ceramic stoichiometric oxide of a bi-metallic alloy doped with aluminum zinc ZAO, the burning voltage of the magnetron discharge is maintained at a level not lower than 600 V. Since the sputtered target should, for the above reasons, be preoxidized and, accordingly, its the surface is a ceramic oxide; when the target surface is sputtered by the incoming ion flow from the region of the magnetron discharge plasma combustion, an additional expenditure of the kinetic energy of incident ions introduced with the sputtering flow occurs to ensure the dissociation of the bonds of the target metal atoms with oxygen atoms when they overcome the near-surface potential barrier. As a result, as it was empirically determined, at voltage values less than 600 V, the kinetic energy of the sputtering plasma ions accelerated in the potential difference of the discharge gap of the magnetron unit will be insufficient to simultaneously ensure the rupture of the oxygen-metal bonds of the surface elements of the sputtered ceramic target of the stoichiometric oxide of the aluminum-doped bi-metal alloy zinc ZAO and knocking out atoms of aluminum Al and zinc Zn from the surface of the target to form a flux of the substance coming to the substrate providing the deposition of the required oxide layer of aluminum-doped zinc Zn-Al-O, which is the first covering layer. Thus, the sputtering of cathode targets from a ceramic stoichiometric oxide of a bi-metallic alloy doped with aluminum zinc ZAO should be carried out at a magnetron discharge burning voltage of at least 600 V.

In addition, restrictions are imposed on the maximum allowable magnetron discharge current, the value of which depends on the material of the sputtered cathode target, as a result of the dependence on the thermal conductivity of the target material. So, for cathode targets made of a bi-metallic alloy doped with aluminum silicon SiAl, the magnetron discharge current should be maintained at a level of no more than 110 A, for cathode targets made of aluminum Al, no more than 160 A, for cathode targets made of a bi-metallic alloy doped with tin zinc ZnSn not more than 60 A, for cathode targets made of a bi-metal alloy doped with aluminum zinc ZnAl not more than 90 A, for cathode targets made of a bi-metal alloy nichrome NiCr, tungsten W and ceramic stoichiometric oxide of a bi-metal alloy doped with aluminum zinc ZAO - not more than 90 A, and for cathode targets made of silver Ag no more than 15 A. These limitations for each of the materials of sputtering cathode targets were empirically revealed based on the observations that when the individual for a particular target material exceeds the limit on the discharge current introduced with the flow sputtering ions from the plasma of a magnetron discharge, the thermal power flux per unit vp at which, for a given ratio of the value of the flux of the incoming heat load per unit time to the value of the thermal conductivity coefficient of a particular material of the cathode target, there will be a dynamic increase in the temperature of the exposed plasma of the target surface, regardless of the efficiency of removing the heat load from the side of the cathode target surface opposite to that , which is directed to the incident flow of radicals from the plasma, with the resultant both cracking of the sputtered cathode target itself directly due to the uneven thermal expansion of the material along the thickness, and local melting of its exposed zone of combustion of the magnetron plasma discharge of the surface and the hit of macro-sized conglomerates of the melted target substance on the glass substrate of the manufactured product , which will lead to its thermomechanical damage and the unusability of the entire previously deposited thin-film structure of the thermally stable highly selective willow energy-saving coating of bronze color on glass.

In this case, the combustion of a magnetron plasma discharge during sputtering is maintained in the pressure range from 1.7⋅10 ^-3 to 4⋅10 ^-2 mbar for all materials of cathode targets. The choice of this range of operating pressures maintained during sputtering is due to the fact that at pressures less than 1.7⋅10 ^-3 mbar the condition of ignition and further stable combustion of a magnetron plasma discharge according to Paschen for the complex of current-voltage characteristics of the discharge inherent in the process of spraying each of the materials of the thin-film layer structure of the article defined and explained above. On the other hand, at pressures above 4⋅10 ^-2 mbar, the mean free path of atoms sputtered from targets immersed in the magnetron discharge plasma will be insufficient for their effective escape from the near-surface region of the target. As a result of the transition of the sputtering process to the over-sputtering mode of the near-streak region of the sputtered target, there will be an actual absence of the flow of the substance sputtered into the substrate arriving at the substrate, as a result of which the deposition of individual layers of the thin-film structure of the thermostable highly selective energy-saving silver-colored coating on glass will be impossible. Based on these two opposing factors, the operating pressures during the processes of target sputtering in the magnetron discharge plasma for all materials of cathode targets should be limited to the range from 1.7⋅10 ^-3 mbar to 4⋅10 ^-2 mbar.

Also, argon Ar acts as a working gas in the process of sputtering all materials of cathode targets. As an inert gas, argon does not contribute to any undesirable reactions during interaction with the sprayed materials. On the other hand, the size and mass of argon Ar atoms are optimal to ensure efficient highly dynamic knocking out of the sputtered material from the targets of all materials used in the described process. In addition, the electronic structure of argon atoms makes it possible to maintain a high ionization density of a substance in a magnetron discharge, characterized by a complex of current-voltage characteristics, the maintenance of which is required to ensure sputtering of the corresponding cathode target material, and which are indicated and explained above.

At the same time, when sputtering targets from a bi-metallic alloy doped with tin zinc ZnSn, a bi-metallic alloy doped with aluminum zinc ZnAl and a bi-metallic alloy nichrome NiCr, a reaction gas component is additionally admitted to the vacuum chamber, which is oxygen O ₂ , which contributes to the formation on the surface of the glass substrate of the required layers of oxide doped with tin zinc Zn-Sn-O, oxide doped with aluminum zinc Zn-Al-O and substoichiometric oxide nichrome Ni-Cr-O, respectively, during the course of the reaction process of oxygen poisoning of target materials. The ratio of the value of the gas supply of oxygen O ₂ to the value of the gas supply of argon Ar in this case should not exceed 1.65. Otherwise, when the total pressure of the working gases in the spray chambers is, as mentioned above, from 1.7⋅10 ^-3 mbar to 4⋅10 ^-2 mbar, the partial ratio between the concentrations of oxygen O ₂ and argon Ar will be shifted towards the excess concentration of oxygen O ₂ to the extent that maintaining the burning current of the sputtering magnetron discharge is less than the permissible limit value for each of the specified target materials - namely: bi-metallic alloy doped with tin zinc ZnSn, bi-metallic alloy doped aluminum zinc ZnAl and bi-metallic alloy nichrome NiCr - will be impossible due to the excessively high degree of poisoning of the surface of the corresponding cathode target.

In turn, when sputtering targets from a bi-metallic alloy doped with aluminum silicon SiAl, from aluminum Al and from tungsten W, a reaction gas component is additionally admitted into the vacuum chamber, which is nitrogen N ₂ , which contributes to the formation of the required substoichiometric nitride layers on the surface of the glass substrate aluminum-doped silicon Si-Al-N, substoichiometric aluminum nitride Al-N and substoichiometric tungsten nitride WN, respectively, during the course of the reaction process of nitrogen poisoning of target materials. The ratio of gazonapuska nitrogen N _{2 of} the largest flow gazonapuska Ar argon thus needs to be maintained so that the ratio of the intensity of the characteristic radiation ionization spray mixture components working gas, which acts as argon Ar, to the intensity of the characteristic radiation ionization basic metal target components in the case of Bi -metallic alloy of aluminum-doped silicon SiAl, which is silicon Si, and the target metal, in the case of monometallic targets made of aluminum Al and tungsten W, respectively, did not exceed 43. Otherwise, as it was empirically determined, the dynamics of side ionization of sputtered targets of atoms of the corresponding substances in the course of their overcoming the combustion zone of the magnetron discharge will be too high for the occurrence of reliable relaxation of the stresses induced by the incident flow of the substance in the growing layers. The latter will lead to the priority removal of the stresses enclosed in the corresponding thin-film layers in the future, during the operation of the final product, and, with the greatest probability, during the course of the process, it is subjected to heat treatment processes that are energetically favorable from the point of view of the redistribution of crystallographic lattice defects, as a result of which cracking and further defoliation of individual layers of substoichiometric aluminum-doped silicon nitride Si-Al-N, substoichiometric aluminum nitride Al-N and substoichiometric tungsten nitride WN coating.

The table below provides an example of a specific implementation of the proposed product. Within the framework of the given example, a series of layer-by-layer depositions of a heat-resistant, highly selective, energy-saving silver-colored coating on the surface of a glass substrate was carried out by sputtering the corresponding materials of sputtering cathode targets in the magnetron discharge plasma while maintaining the parameters of the sputtering processes in the ranges indicated in the table. The thickness of the substrate used was 6 mm. The work was carried out on an industrial installation for in-line ion-plasma deposition of thin-film coatings from magnetron discharge plasma on Von Ardenne GC330H glass. The limiting residual pressure in the spray chambers of the installation was 2.78⋅10 ^-6 mbar.

The sequence of layer materials, as well as the corresponding target materials used for their deposition, are shown in ascending order from the surface of the glass substrate outward.

In total, 16 samples of coatings were obtained within the described series.

The thicknesses of individual layers of individual materials for each of the obtained samples were maintained at the same level, as indicated in the table, by means of intermediate in-situ monitoring of the spectrophotometric characteristics of the forming layer structure with adjustment by the time-of-flight parameter. As can be seen from the table, obtained for the described series of layer thicknesses and their ratios satisfy the limits indicated in the claims. The corresponding materials and target composition (or impurity purity for single-element targets) used in the process of sputtering in the magnetron discharge plasma are similarly satisfied with the method described in the claims of the present invention for producing a thermally stable highly selective energy-saving silver-colored coating on glass.

The registered working pressure of the gas mixture in the spray chambers of the installation during the deposition of each of the layers was for each of the samples of the series within the limits indicated in the table and corresponding to the acceptable range according to the formula of the present invention. In turn, the combustion voltage of the sputtering magnetron discharge and the discharge current for each of the coating layers within the described series were varied between the samples of the series by adjusting the output power level at the discharge power supply. The ranges of values of the combustion voltage and the current strength of magnetron discharges, which were maintained within the entire described series for the deposition of the corresponding layers of a multilayer thin-film structure, are also given in the table. As you can see, for each of the materials used for the sputtering cathode targets, they correspond to the claims.

Argon Ar was used as a working gas for sputtering each of the used cathode targets. At the same time, for the deposition of oxide layers during the sputtering of targets from a bi-metallic alloy doped with tin zinc ZnSn, a bimetallic alloy doped with aluminum zinc ZnAl and a bi-metallic alloy nichrome NiCr, a reaction gas component was additionally admitted into the sputtering vacuum chambers, which was oxygen O ₂ . In turn, for the deposition of nitride layers during sputtering of targets from a bi-metallic alloy doped with aluminum silicon SiAl, from aluminum Al and from tungsten W, a reaction gas component was additionally admitted into the sputtering vacuum chambers, which was nitrogen N ₂ . The control of the leakage flow value during the filling of each of the components of the gas mixture was maintained using MKS P2A gas flow meters. In this case, in accordance with the formula of the invention, the ratio of the value of the gas injection of oxygen O ₂ to the value of the gas injection of argon Ar was maintained at a level not exceeding 1.65, and reflected for the case of deposition by sputtering in the plasma of a magnetron discharge of each corresponding material in the table, and the ratio of the value gas injection of nitrogen N ₂ to the value of the flow of gas injection of argon Ar was maintained in such a way that, also given for each specific material of the sputtered cathode target and the corresponding deposited coating layer in the table, the ratio of the intensity of the characteristic radiation of ionization of the spray component of the mixture of working gases, which is argon Ar , to the intensity of the characteristic radiation of ionization of the main metal component of the target in the case of a bimetallic alloy of aluminum-doped silicon SiAl, which is silicon Si, and the target metal, in the case of monometallic targets made of aluminum Al and tungsten and W, respectively, did not exceed 43. Monitoring and stabilization of the radiation intensity of the corresponding characteristic spectral lines of sputtering magnetron plasma discharges were carried out using the Von Ardenne VAPROCOS PEM V2 plasma optical emission registration system connected via an analog-digital feedback loop to the gas flow meters of the nitrogen inlet N ₂ -components of a mixture of working gases MKS P2A.

The obtained samples were subjected to thermal action as a result of holding in laboratory muffle furnaces Carbolite GLO 11-1G at a temperature of 800 ° C for 17 minutes each. Subsequent analysis of the turbidity of the samples by calculating the turbidity value based on the assessment of the standard deviation of the intensity value of the chromaticity index of the unit area of the sample surface from the sample over the full surface in monochrome display, an example of which is shown in Fig. 1, demonstrated that for all 16 obtained samples the turbidity value does not exceed 0.0973%.

The transmission spectra for all 16 samples obtained within the described series of products in the UV / VIZ / IR range of electromagnetic radiation wavelengths of 250-1500 nm are shown in Fig. 2. The spectrum shows a sharp drop in intensity along the spectral transmission curve when going from the wavelength range of visible radiation to the near-IR range of thermal solar radiation in the region of the order of 1000 nm, which is characteristic of highly selective products of thin-film deposition of energy-efficient coatings on glass with two reflecting IR-radiation layers. due to which an effective prevention of the transmission of excess thermal solar radiation at wavelengths exceeding 1200 nm is provided. Along with this, the graphs of the transmission spectra reach saturation with the asymptotic tendency of the intensity to zero along the abscissa, which indicates the quality of energy efficiency in terms of reducing the radiative heat loss with a correspondingly low emissivity of the samples. The numerical determination of the integral parameters of the obtained spectra gives the following set of ranges of the obtained characteristic values for the analyzed samples of the series: the transmittance of visible radiation T _vis , ranging from 46% to 52%, the solar factor g, ranging from 28% to 30%, selectivity S, ranging from 1.528 to 1.831 units, the coefficient of direct transmission of electromagnetic radiation in the range 385-790 THz, ranging from 0.49 to 0.55 fractions.

To determine the numerical normalization of the qualities of energy efficiency from the point of view of reducing radiative heat losses in cold weather of the samples, contactless stratometry of the coating surface was used, followed by spectroscopy of the far infrared region on a Fourier transform IR spectrophotometer (FT-IR). According to the results of stratometric measurements, the surface ohmic resistance of the thin-film coating for all samples, given by the total thickness of the layers of silver Ag, was 1.99 Ohm / square before heat treatment in muffle furnaces, and 1.56 Ohm / square after heat treatment in muffle furnaces, respectively. In this case, the direct determination of the corresponding emissivity of the product samples, as an integral parameter of the resulting FT-IR spectrum, gives for all the samples obtained an ε value equal to 0.02 before heat treatment and 0.01 after heat treatment, which corresponds to the specified technical result.

The colorimetry of the samples in reflection from the side of the substrate, opposite to the side on which the thin-film energy-efficient optical coating is applied, in the a * / b * plane of the international standard CEILAB (D65 / 10) (an example of analysis is shown in Fig. 3) gives the following values for color quasi coordinates: position along the axis of color differentiation green / red of the quasi-coordinate grid a *, ranging from -4.16 to -2.97 units; position on the axis of color differentiation yellow / blue of the quasi-coordinate grid b *, ranging from -1.40 to -1.18 units.

As another example of a specific implementation of the proposed product, a series of layer-by-layer depositions of a heat-resistant, highly selective, energy-saving silver-colored coating on the surface of a glass substrate was carried out by sputtering corresponding materials of sputtering cathode targets in the magnetron discharge plasma while maintaining the parameters of the sputtering processes in the ranges indicated in the table below. Similarly to the first example, the thickness of the substrate used was 6 mm, and the work was carried out on an industrial installation for in-line ion-plasma deposition of thin-film coatings from magnetron discharge plasma on Von Ardenne GC330H glass. The limiting residual pressure in the spray chambers of the installation was 3.25⋅10 ^-6 mbar.

The sequence of layer materials, as well as the corresponding target materials used for their deposition, are shown in ascending order from the surface of the glass substrate outward.

In total, within the described series, 7 samples of coatings were obtained. The thicknesses of individual layers of individual materials varied between the produced samples within the ranges shown in the table by changing the time-of-flight parameter of the substrate supply with an intermediate registration of the actual thicknesses through in-situ monitoring of the spectrophotometric characteristics of the forming layer structure. As can be seen from the table, the thicknesses of the individual layers and their ratios within the ranges used for the described series of the ranges satisfy the limits indicated in the claims. At the same time, to assess the effect of the composition of the spray targets used in the preparation of individual layers of the described coating on the quality and characteristics of the resulting products, in the manufacture of individual samples of the series, we used sputtering cathode targets with different partial compositions (or impurity purity for the cases of monoelement targets), selected from the corresponding ranges shown in the table for each of the functional layers of the thin-film coating, and also satisfying the method described in the claims of the present invention for obtaining a heat-resistant highly selective energy-saving silver-colored coating on glass.

The registered working pressure of the gas mixture in the spray chambers of the installation during the deposition of each of the layers was for each of the samples of the series within the limits indicated in the table and corresponding to the acceptable range according to the formula of the present invention. In turn, the combustion voltage of the sputtering magnetron discharge and the discharge current for each of the coating layers within the described series were maintained at the same level by adjusting the output power at the discharge power source with parallel adjustment of the balance of gas injection flows of the components of the working gas mixture corresponding to the deposited material. The values of the combustion voltage and the current strength of magnetron discharges, which were maintained within the entire described series for the deposition of the corresponding layers of a multilayer thin-film structure, are also given in the table. As you can see, for each of the materials used for the sputtering cathode targets, they correspond to the claims.

Argon Ar was used as a working gas for sputtering each of the used cathode targets. At the same time, for the deposition of oxide layers during the sputtering of targets from a bi-metallic alloy doped with tin zinc ZnSn, a bimetallic alloy doped with aluminum zinc ZnAl and a bi-metallic alloy nichrome NiCr, a reaction gas component was additionally admitted into the sputtering vacuum chambers, which was oxygen O ₂ . In turn, for the deposition of nitride layers during sputtering of targets from a bi-metallic alloy doped with aluminum silicon SiAl, from aluminum Al and from tungsten W, a reaction gas component was additionally admitted into the sputtering vacuum chambers, which was nitrogen N ₂ . The control of the leakage flow value during the filling of each of the components of the gas mixture was maintained using MKS P2A gas flow meters. In this case, in accordance with the formula of the invention, the ratio of the value of the gas injection of oxygen O ₂ to the value of the gas injection of argon Ar was maintained at a level not exceeding 1.65, and reflected for the case of deposition by sputtering in the plasma of a magnetron discharge of each corresponding material in the table, and the ratio of the value gas injection of nitrogen N ₂ to the value of the flow of gas injection of argon Ar was maintained in such a way that, also given for each specific material of the sputtered cathode target and the corresponding deposited coating layer in the table, the ratio of the intensity of the characteristic radiation of ionization of the spray component of the mixture of working gases, which is argon Ar , to the intensity of the characteristic radiation of ionization of the main metal component of the target in the case of a bimetallic alloy of aluminum-doped silicon SiAl, which is silicon Si, and the target metal, in the case of monometallic targets made of aluminum Al and tungsten and W, respectively, did not exceed 43. Monitoring and stabilization of the radiation intensity of the corresponding characteristic spectral lines of sputtering magnetron plasma discharges were carried out using the Von Ardenne VAPROCOS PEM V2 plasma optical emission registration system connected via an analog-digital feedback loop to the gas flow meters of the nitrogen inlet N ₂ -components of a mixture of working gases MKS P2A.

Each of the samples was cut into two parts, one of which was used for characterization analyzes, and the other was subjected to tests for thermal quenching of the substrate, followed by its connection to an additional transparent substrate facing the outer coating layer containing zinc-doped tin oxide Zn-Sn -O, and further comparative characterization as described below.

The first part of the specimen cuts, intended for characterization analyzes, was subjected to temperature exposure as a result of exposure in laboratory Carbolite GLO 11-1G muffle furnaces at 800 ° C for 17 minutes for each individual cut. Subsequent analysis of the turbidity of the samples by calculating the turbidity value based on the assessment of the standard deviation of the intensity value of the chromaticity index of the unit area of the sample surface from the sample over the full surface in monochrome display, an example of which is presented in Fig. 4, demonstrated that for all 7 obtained samples the turbidity value does not exceed 0.0958%.

The transmission spectra for all 7 samples obtained within the framework of the described exemplary series of products in the UV / VIZ / IR wavelength range of electromagnetic radiation of 250-1500 nm are shown in Fig.5. The spectrum shows a sharp drop in intensity along the spectral transmission curve when going from the wavelength range of visible radiation to the near-IR range of thermal solar radiation in the region of the order of 1000 nm, which is characteristic of highly selective products of thin-film deposition of energy-efficient coatings on glass with two reflecting IR-radiation layers. due to which an effective prevention of the transmission of excess thermal solar radiation at wavelengths exceeding 1200 nm is provided. Along with this, the graphs of the transmission spectra reach saturation with the asymptotic tendency of the intensity to zero along the abscissa, which indicates the quality of energy efficiency in terms of reducing the radiative heat loss with a correspondingly low emissivity of the samples. The numerical determination of the integral parameters of the obtained spectra gives the following set of ranges of the obtained characteristic values for the analyzed samples of the series: the transmittance of visible radiation T _vis , ranging from 48% to 51%, the solar factor g, ranging from 26% to 29%, selectivity S, ranging from 1.655 to 1.961 units, the coefficient of direct transmission of electromagnetic radiation in the range 385-790 THz, ranging from 0.44 to 0.51 fractions.

To determine the numerical normalization of the qualities of energy efficiency from the point of view of reducing radiative heat losses in cold weather of the samples, contactless stratometry of the coating surface was used, followed by spectroscopy of the far infrared region on a Fourier transform IR spectrophotometer (FT-IR). According to the results of stratometric measurements, the surface ohmic resistance of a thin-film coating, specified by the total thickness of the silver layers Ag, was for all samples the range of values from 1.94 Ohm / square to 2.07 Ohm / square before heat treatment in muffle furnaces, and from 1.43 Ohm / square up to 1.58 Ohm / square after heat treatment in muffle furnaces, respectively. In this case, the direct determination of the corresponding emissivity of the product samples, as an integral parameter of the resulting FT-IR spectrum, gives for all the samples obtained an ε value equal to 0.02 before heat treatment and 0.01 after heat treatment, which corresponds to the specified technical result.

Colorimetry of samples in reflection from the side of the substrate, opposite to the side on which the thin-film energy-efficient optical coating is applied, in the a * / b * plane of the international standard CEILAB (D65 / 10 °) - an example of the analysis is presented in Fig. 6 - gives the following values for color quasi coordinates : position along the axis of color differentiation green / red of the quasi-coordinate grid a *, ranging from -3.65 to -3.13 units; position along the axis of color differentiation yellow / blue of the quasi-coordinate grid b *, ranging from -1.49 to -1.44 units.

At the same time, joining the product with a heat-resistant highly selective energy-saving silver-colored coating on a thermally hardened glass substrate with an additional transparent substrate facing the outer layer of the coating containing zinc-doped tin oxide Zn-Sn-O, on the one hand, made it possible to increase the chemomechanical stability of the thin-film coating, and on the other hand, demonstrated the retention of the ranges of the resulting characteristic values obtained during the experiments and reflected above, obtained by characterizing products by UV / VIZ / IR and FT-IR spectrophotometry, non-contact stratometry and colorimetry in reflection from the side of the substrate opposite the side, on which the thin-film energy-efficient optical coating is applied, in the a * / b * plane of the international standard CEILAB (D65 / 10 °). In this case, thermal quenching of a glass substrate with a heat-resistant, highly selective, energy-saving silver-colored coating applied to its surface was carried out in a Glastone FC 500 industrial tempering furnace for flat glass at a heating temperature of 670 ° C for 75 sec. with a uniform convection profile. The temperature profiles along the upper and lower surfaces of the substrate relative to the transfer shafts of the furnace had a dome-shaped distribution with the "left edge-center-right edge" exposure: 670-672-658 along the upper surface; 660-668-650 lower border. The air balance was 65%, the nozzle opening was 34 mm. Flat-polished float glass M1 with a thickness of 4 mm was used as an additional transparent substrate facing the outer coating layer containing zinc-doped tin oxide Zn-Sn-O. In this case, the fixation of the connected substrates of the products was carried out with a rigid aluminum frame with its subsequent filling along the edge with a polymer compound to seal the glass unit assemblies along the entire end surface of the combined substrates.

Thus, on the basis of the foregoing, the presented article with a heat-resistant highly selective energy-saving silver-colored coating on glass, implemented according to the above method, demonstrates the simultaneous manifestation of the qualities of heat resistance of an energy-saving coating on glass substrates, allowing the implementation of thermal hardening, heat-strengthening and thermally-assisted bending, and expressed in retention of the turbidity value of a glass substrate with an energy-efficient coating after exposure to temperatures at a level not higher than 9.8⋅10 ^-2 % at permissible exposure temperatures not lower than 780 ° C for a duration of at least 15 minutes; as well as the silver color of the energy-saving coating on glass substrates in the case of light reflection from the surface of the glass substrate on the side opposite to the side on which the thin-film energy-efficient optical coating is applied, achieved in a wide range of viewing angles and characterized by the following reflection shade in color quasi-coordinates a * / b * international standard CEILAB (D65 / 10): a * from -5 to -0.5, and b * from -5.2 to +2.5; and high selectivity of an energy-saving coating on glass substrates, characterized by a selectivity S of not less than 1.384 with a corresponding transmittance of visible radiation T _{vis of} at least 42% and an emissivity of the product specified by the surface ohmic resistance of a thin-film coating not exceeding 2.6 Ohm / square.

Claims (4)

1. A heat-resistant, highly selective, energy-saving, silver-colored coating on glass, consisting of separate, directly contacting layers, characterized in that the coating includes the following adjacent layers in the order of listing from the glass substrate to the outside: the first layer adjacent to the surface of the glass substrate contains a substoichiometric aluminum-doped silicon nitride Si-Al-N, the subsequent layer being the first contact layer that contains tin-doped zinc oxide Zn-Sn-O, followed by a layer containing aluminum-doped zinc oxide Zn-Al-O, which is the first catalytic layer , the next layer, which contains silver Ag, is the first layer reflecting infrared radiation, followed by a layer containing substoichiometric nichrome oxide Ni-Cr-O, which is the first barrier layer, the next layer which contains aluminum-doped zinc oxide Zn-Al -O, is the first covering layer behind this is followed by an intermediate layer containing substoichiometric aluminum nitride Al-N, the subsequent layer is the second contact layer and contains tin-doped zinc oxide Zn-Sn-O, followed by a layer containing aluminum-doped zinc oxide Zn-Al-O, which is the second catalytic layer, the subsequent layer which contains silver Ag is the second infrared reflective layer, followed by the layer containing substoichiometric nichrome oxide Ni-Cr-O which is the second barrier layer, the next layer which contains substoichiometric tungsten nitride WN is absorbing layer, followed by a layer containing substoichiometric aluminum nitride Al-N, which is the second covering layer, as well as a protective layer to provide chemomechanical protection of the entire previously listed layer structure, the next layer, which is the outer layer of the entire structure of the coating layers and acts as a crack propagation "PRT" - layer i, contains zinc-doped tin oxide Zn-Sn-O, while the thickness of the intermediate layer containing substoichiometric aluminum nitride Al-N is from 57 to 68 nm, and the thickness of the layer containing substoichiometric aluminum-doped silicon nitride Si-Al-N, is from 17 to 21 nm, with the ratio of the thickness of the layer containing substoichiometric aluminum-doped silicon nitride Si-Al-N to the total thickness of the second covering layer containing substoichiometric aluminum nitride Al-N and the outer layer containing zinc-doped tin oxide Zn -Sn-O, is in the range from 0.3 to 0.7, in addition, the total thickness of two layers reflecting infrared radiation containing silver Ag is such that the resulting surface ohmic resistance of the heat-resistant highly selective energy-saving silver-colored coating on glass does not exceed 2 , 19 Ohm / square, with the ratio of the thickness of the first infrared reflecting layer containing silver Ag to the thickness of the second infrared reflecting layer containing silver Ag is from 0.21 to 0.38, while the ratio of the thickness of the first barrier layer, which contains the substoichiometric oxide of nichrome Ni-Cr-O, to the total thickness of the first contact layer containing oxide doped with tin zinc Zn-Sn-O, and the first catalytic layer containing oxide doped with aluminum zinc Zn-Al-O, and the ratio of the thickness of the second barrier layer, which contains substoichiometric oxide of nichrome Ni-Cr-O, to the total thickness of the second the contact layer containing tin-doped zinc oxide Zn-Sn-O and the second catalytic layer containing aluminum-doped zinc oxide Zn-Al-O are from 0.19 to 0.52, and the ratio of the thickness of the second barrier layer, which contains substoichiometric nichrome oxide Ni-Cr-O, to the thickness of the first barrier layer containing substoichiometric nichrome oxide Ni-Cr-O is from 0.4 to 11.6, while the ratio of the thickness of the first th contact layer containing tin-doped zinc oxide Zn-Sn-O to the thickness of the first catalytic layer containing aluminum-doped zinc oxide Zn-Al-O and the thickness of the second contact layer containing tin-doped zinc oxide Zn-Sn-O, to the thickness of the second catalytic layer containing aluminum-doped zinc oxide Zn-Al-O is from 0.18 to 15.65, while the thickness of the absorbing layer, which contains substoichiometric tungsten nitride WN, is such that the resulting direct transmission of electromagnetic radiation in the range 385 -790 THz of heat-resistant, highly selective, energy-saving silver-colored coating on glass is from 0.43 to 0.55, while the ratio of the thickness of the outer "PRT" layer containing zinc-doped tin oxide Zn-Sn-O to the thickness of the first covering layer containing aluminum-doped zinc oxide Zn-Al-O, is not less than 1.4, and the thickness of the outer "PRT" -layer containing zinc-doped tin oxide Zn- Sn-O is not less than 4 nm, while the total thickness of the second covering layer, which contains substoichiometric aluminum nitride Al-N, and the outer "PRT" -layer containing zinc-doped tin oxide Zn-Sn-O, is not less than 24 nm. 2. A heat-resistant, highly selective, energy-saving silver-colored coating on glass according to claim 1, characterized in that the glass substrate with a multilayer coating applied to its surface, previously thermally hardened, is connected to at least one additional transparent substrate, which faces the outer coating layer containing zinc-doped tin oxide Zn-Sn-O. 3. A heat-resistant, highly selective, energy-saving silver-colored coating on glass according to claim 1, characterized in that the glass substrate with a multilayer coating applied to its surface, previously heat-hardened, is connected to at least one additional transparent substrate that faces the outer coating layer containing zinc-doped tin oxide Zn-Sn-O. 4. A method of obtaining a heat-resistant, highly selective, energy-saving silver-colored coating on glass according to claim 1, including applying in a vacuum chamber directly to the surface of the glass base from one of its sides contacting layers, characterized in that the deposition occurs by spraying materials in the magnetron discharge plasma sputtering cathode targets in the following sequence: bi-metal alloy of aluminum-doped silicon SiAl with a doping level of 2 to 60%, bimetallic alloy of tin-doped zinc ZnSn with a doping level of 5 to 80%, bi-metal alloy of aluminum doped zinc ZnAl with a degree of alloying ranging from 5 to 80%, silver Ag with an impurity purity of at least 90%, a bi-metallic alloy of nichrome NiCr with a partial concentration of nickel not less than 10%, ceramic stoichiometric oxide of a bimetallic alloy doped with aluminum zinc ZAO with a degree doping from 5 to 80%, aluminum Al with an impurity purity of at least 84%, bi-metallic alloy doped with tin zinc ZnSn with a degree of doping ranging from 5 to 80%, bi-metallic alloy doped with aluminum zinc ZnAl with a degree of alloying from 5 to 80%, silver Ag with an impurity purity of not less than 90%, a bi-metallic alloy of nichrome NiCr with a partial concentration of nickel of not less than 10%, tungsten W with an impurity purity of not less than 93%, aluminum Al with an impurity purity of not less than 84% and a bi-metallic alloy of tin-doped zinc ZnSn with a degree of doping ranging from 5 to 80%, while the burning voltage of the magnetron discharge during sputtering of cathode targets from a bi-metallic alloy of aluminum-doped silicon SiAl and from aluminum Al is maintained in the range from 420 to 560 B, when sputtering cathode targets from a bi-metallic alloy doped with tin zinc ZnSn and from a bi-metallic alloy doped with aluminum zinc ZnAl - in p in the range from 420 to 510 V, when sputtering cathode targets made of a bi-metallic alloy of nichrome NiCr and tungsten W - in the range from 550 to 610 V, when sputtering cathode targets made of silver Ag, the burning voltage of a magnetron discharge does not exceed 480 V, and when sputtering cathode targets made of ceramic stoichiometric oxide of a bi-metallic alloy doped with aluminum zinc ZAO; the combustion voltage of the magnetron discharge is maintained at least 600 V; the discharge current does not exceed the following limits: for cathode targets made of a bimetallic alloy doped with aluminum silicon SiAl no more than 110 A, for cathode targets made of aluminum Al no more than 160 A, for cathode targets made of a bimetallic alloy doped with tin zinc ZnSn no more than 60 A, for cathode targets made of a bi-metal alloy doped with aluminum zinc ZnAl not more than 90 A, for cathode targets made of a bi-metal alloy nichrome NiCr, tungsten W and ceramic stoichiometric oxide of a bi-metal alloy doped with aluminum zinc ZAO - not more than 90 A, for cathode targets made of silver Ag is not more than 15 A; in this case, the combustion of a magnetron plasma discharge during sputtering is maintained in the pressure range from 1.7⋅10 ^-3 to 4⋅10 ^-2 mbar for all materials of cathode targets, and argon Ar acts as a working gas, while when sputtering targets from bi- metal alloy doped with tin zinc ZnSn, bimetallic alloy doped with aluminum zinc ZnAl and bi-metallic alloy nichrome NiCr, a reaction gas component is additionally admitted into the vacuum chamber, which is oxygen O ₂ , and the ratio of the amount of gas supply of oxygen O ₂ to the value of the gas supply of argon Ar does not exceed 1.65, and when sputtering targets from a bi-metal alloy doped with aluminum silicon SiAl, from aluminum Al and from tungsten W, a reaction gas component is additionally admitted into the vacuum chamber, which is nitrogen N ₂ , and the ratio of the amount of nitrogen gas injection N ₂ to the value of the argon gas injection flow Ar is maintained in such a way , so that the ratio of the intensity of the characteristic radiation of ionization of the sputtering component of the working gas mixture, which is argon Ar, to the intensity of the characteristic radiation of ionization of the main metal component of the target in the case of a bi-metallic alloy of aluminum-doped silicon SiAl, which is silicon Si, and the target metal , in the case of monometallic targets made of aluminum Al and tungsten W, respectively, did not exceed 43.

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