RU2728005C1 - Heat-resistant highly selective energy-saving bronze color 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. In particular, a heat-resistant highly selective energy-saving coating of bronze color on glass is proposed, which consists of separate directly contacting layers. Said coating includes the following adhering layers in the order from the glass substrate to the outside: the first layer containing the sub-stoichiometric nitride of silicon-doped Si-Al-N, the next layer being the first contact layer, which contains tin-doped zinc oxide Zn-Sn-O, followed by a layer containing zinc alloyed zinc oxide Zn-Al-O, which is the first catalytic layer, next layer, which contains Ag silver, is the infrared reflecting first layer, followed by a layer comprising a sub-stoichiometric nichrome oxide Ni-Cr-O, which is a first barrier layer, next layer, which contains Zn-Al-O zinc alloyed aluminum, is first covering layer, followed by an intermediate layer containing sub-stoichiometric aluminum nitride Al-N, next layer is second contact layer and contains tin-doped zinc oxide Zn-Sn-O, followed by a layer containing zinc alloyed zinc oxide Zn-Al-O, which is a second catalyst layer, next layer, which contains silver Ag, is the second layer reflecting infrared radiation, followed by a layer comprising a sub-stoichiometric nichrome Ni-Cr-O oxide, which is a second barrier layer, next layer, which contains sub-stoichiometric tungsten nitride W-N, is absorbing layer, followed by a layer containing sub-stoichiometric aluminum nitride Al-N, which is a second covering layer, as well as a protective layer for providing chemomechanical protection of the entire previously listed layer structure, next layer, which is an external layer of the above listed structure of the coating layers and acting as an anti-propagation cracks "PRT" layer, contains zinc alloyed zinc Zn-Sn-O.EFFECT: technical result consists in provision of stability in relation to prolonged effects of high temperatures, which is expressed in maintaining minimum value of turbidity level of glass substrate based on results of exposure, sun-proof properties with respect to excessive thermal solar action with simultaneous maintenance of a satisfactory visible light transmission level, properties of energy efficiency in terms of reducing radiative heat losses during cold and bronze 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, achieved in a 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 reduce 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 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 deposited lower dielectric layers / a layer of silver Ag or copper Cu / upper dielectric layer or a set of successively deposited 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 solar thermal radiation, since they do not demonstrate a sufficient reduction in 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 criteria for energy savings 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 patents No. 2415968, No. 2636995. 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 wavelength range, while maintaining a relatively high level of visible light transmission. which is realized due to interference processes occurring during 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 window 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 hardening 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 preform 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 to actually quench and / or bend.

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 locally appearing as discrete areas or spots.

а* от +1 до +9, и b* от +8 до +14;.Of the known energy efficient thin-film deposition products on glass substrates, 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. Examples of such a product are the coatings described in RF patents No. 2421419 and No. 2666809. Also, the choice of products of thin-film deposition on glass is extremely limited, which simultaneously have 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 exhibit the desired hue 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 needs 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 bronze tint 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

a * from +1 to +9, and b * from +8 to +14 ;.

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 bronze color of the 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. 2563527, which describes a product with an energy-saving bronze-colored coating, including one layer reflecting IR radiation, the first and second layers containing silicon nitride, and the ratio of the thickness of the first layer to the thickness of the second layer is 0.45-0.90. The product has a reflective bronze color on the glass surface in combination with the specified solar control properties and transmission parameters presented in the table below. The coated product is designed so that the reflected color of the glass surface is characterized by certain parameters: red a * and yellow b *.

In this case, according to the description, the preferred method of obtaining the described article according to this invention is the deposition of all coating layers by sputtering on a glass substrate, namely sputtering from ion sputtering targets.

In addition, as noted in the dependent claim 9 of the claims of the said invention, and is further disclosed by the authors in the description, the proposed coated article can be subjected to heat treatment, coupled with heating the coated substrate to a temperature of from 500 ° C to 800 ° C (more preferably from about 580 ° C to 750 ° C) for a sufficient period of time, for example from 1 to 15 minutes, in order to achieve the desired result, for example, heat hardening, bending and / or heat hardening.

However, this product, and the aforementioned preferred method of its manufacture, do not 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 value of solar heat gain, and also does not allow at the same time to achieve resistance to heat treatment under conditions required for modern technological applications of glass processing, characterized by permissible exposure durations exceeding 15 minutes.

а* от +0,6 до +9,5, и b* от +7,7 до +14,6; и высокой селективности энергосберегающего покрытия на стеклянных подложках, характеризуемой величиной селективности S не менее 1,346 при соответствующих коэффициенте пропускания видимого излучения T_vis, составляющим не менее 37%, и величине излучательной способности изделия, задаваемой поверхностным омическим сопротивлением тонкопленочного покрытия, не превышающим 2,4 Ом/□.The technical result of the present invention is aimed at the simultaneous provision 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 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 9.4 ⋅10 ^-2 % at permissible exposure temperatures of at least 780 ° C for at least 15 minutes; as well as the bronze color of an energy-saving coating on glass substrates 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 in color quasi-coordinates a * / b * international standard CEILAB

a * from +0.6 to +9.5, and b * from +7.7 to +14.6; and a high selectivity of an energy-saving coating on glass substrates, characterized by a selectivity S of at least 1.346 with a corresponding transmittance of visible radiation T _{vis of} at least 37% and an emissivity of the product specified by the surface ohmic resistance of a thin-film coating not exceeding 2.4 Ohm / □.

The technical result is achieved by the fact that a heat-resistant, highly selective, energy-saving bronze-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 a substoichiometric oxide of nichrome 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 next layer, which is the outer layer of the entire structure of the coating layers and plays the role of "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 352 nm to 57 nm, and the thickness of the layer containing the substoichiometric aluminum-doped silicon nitride Si-Al-N is from 21 nm to 32 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, 8 to 1.7, 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 bronze-colored coating on glass does not exceed 2.27 Ohm / □, 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 from radiation, containing silver Ag, is from 0.29 to 0.41, while the ratio of the thickness of the first barrier layer, which contains 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 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 oxide doped with aluminum zinc Zn-Al-O are from 13⋅10 ^-3 to 0.27, 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 1.3 to 12.5, while the ratio of the thickness of the first contact layer containing the doped oxide zinc tin 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 the oxide doped with aluminum zinc Zn-Al-O, range from 0.56 to 24.25, 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 a heat-resistant highly selective energy-saving coating bronze color on glass is from 0.36 to 0.53, while the ratio of the thickness of the outer "PRT" -layer containing oxide doped with zinc tin Zn-Sn-O to the thickness of the first covering layer containing oxide doped with aluminum zinc Zn-Al -O, is at least 0.7, and the thickness of the outer "SPT" -layer containing zinc-doped tin oxide Zn-Sn-O is at least 7 nm, while the total thickness 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 20 nm.

In addition, in a particular case, it is proposed to join a glass substrate previously subjected to additional thermal hardening with a multilayer coating applied to its surface with at least one additional transparent substrate that faces 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 bronze-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:

bimetallic alloy doped with aluminum silicon SiAl with a degree of alloying ranging from 2% to 60%;

bimetallic alloy doped with tin zinc ZnSn with an alloying degree of 5% to 80%;

bimetallic alloy alloyed with aluminum zinc ZnAl with an alloying degree of 5% to 80%;

silver Ag with an impurity purity of at least 87%;

bimetallic alloy of nichrome NiCr with a partial concentration of nickel not less than 10%;

ceramic stoichiometric oxide of bimetallic 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%;

bimetallic alloy doped with tin zinc ZnSn with an alloying degree of 5% to 80%;

bimetallic alloy alloyed with aluminum zinc ZnAl with an alloying degree of 5% to 80%;

silver Ag with an impurity purity of at least 87%;

bimetallic alloy of nichrome NiCr with a partial concentration of nickel not less than 10%;

tungsten W with an impurity frequency of at least 93%;

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

bimetallic alloy doped with tin zinc ZnSn with an alloying degree of 5% to 80%;

in this case, the burning voltage of the magnetron discharge during sputtering of cathode targets from a bimetallic alloy of aluminum-doped silicon SiAl and from aluminum Al is maintained in the range from 420 to 610 V, when sputtering cathode targets from a bimetallic alloy doped with tin zinc ZnSn and from a bimetallic alloy doped with aluminum zinc ZnAl - in the range from 420 to 545 V, when sputtering cathode targets made of a bimetallic alloy of nichrome NiCr and tungsten W - in the range from 550 to 670 V, when sputtering cathode targets made of silver Ag, the burning voltage of a magnetron discharge does not exceed 560 V, and when sputtering cathode targets targets made of ceramic stoichiometric oxide of bimetallic 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 bimetallic alloy doped with aluminum zinc ZnAl not more than 90 A, for cathode targets made of bimetallic alloy nichrome NiCr, tungsten W and ceramic stoichiometric oxide of bimetallic alloy doped with aluminum zinc ZAO - no more than 90 A, for cathode targets made of silver Ag no more than 15 A; In this case, the combustion of a magnetron plasma discharge during sputtering is maintained in the pressure range from 11⋅10 ^-4 to 4⋅10 ^-2 mbar for all materials of cathode targets, and argon Ar acts as a working gas, while sputtering targets made of a bimetallic alloy doped with tin zinc ZnSn, bimetallic alloy doped with aluminum zinc ZnAl and bimetallic 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 1.86, and When sputtering targets made of a bimetallic alloy of aluminum-doped silicon SiAl, aluminum Al and 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 gas inlet of nitrogen N ₂ to the amount of gas inlet of argon Ar is maintained in this way so that is the ratio of the intensity of the characteristic radiation of ionization of the sputtering component of a 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 W, respectively, did not exceed 54.

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 "cross-linking" 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 mainly 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 a 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 reflective layers containing silver Ag, thus achieving the desired sunscreen properties in relation to excessive solar thermal exposure, as well as energy efficiency qualities with from the point of view of reducing radiative heat losses in cold weather, corresponding to the value of the emissivity of the product, given by the surface ohmic resistance of the thin-film coating, not exceeding 2.27 Ohm / □. 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 the heating of the substrate during heat treatment - in mainly sodium, magnesium, calcium and their oxides. This, in turn, prevents the entry of the listed 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 local, initiated by reaction processes on diffusing radicals, aggregation of conductive thin-film optical layers can occur. 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 adjoining 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 the individual layers of the thin-film coating of the article, which is necessary to ensure its structural integrity and mechanical resistance to external influences during use.

In this case, 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, directly 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 a reflective surface is covered with a non-reflective film to split the beam of 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 radiation of silver Ag), in 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 uniform 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 oxide doped with tin zinc 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 2.4 Ohm / □, 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 bimetal 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 aluminum-doped zinc oxide 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 aluminum-doped silicon nitride Si-Al-N adjacent to the surface of the glass substrate showed 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, the oxide layer doped with tin zinc Zn-Sn-O, as a contact layer adjacent to the surface of the glass substrate. 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 above empirical observations, a sequence of functionally separated contact and catalytic layers, pre-deposited by the IR-reflecting Ag layer of silver, 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, which persists 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 that reflect IR radiation and contain 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, in 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.

а* от +0,6 до +9,5, и b* от +7,7 до +14,6.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-reflective 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. Within the scope of the present invention, as both the first and second barrier layers applied directly over the first and second infrared reflecting layers containing silver Ag, respectively, layers containing a substoichiometric nichrome oxide Ni — Cr — O were chosen. 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, which contribute to the implementation of the thermal stability of the described coating on glass declared within the framework of 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-reflecting 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 makes it possible to achieve the claimed in the technical problem of the present invention a combination of the level of selectivity of a thin-film optical coating on a glass substrate S and the value of the integral super-transmission of visible radiation T _vis in the range of not less than 1.346 and 37%, 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 the 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 bronze 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

a * from +0.6 to +9.5, and b * from +7.7 to +14.6.

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 oxygen-deficient silver Ag and nichrome layers, 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 the 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 transparency and heat reflection. Similarly, in order to minimize the final additional reduction 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, aluminum-doped zinc oxide Zn-Al-O, which meets the above requirements, was chosen as the material of the first covering layer of the thin-film optical energy-saving coating of the product.

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, while maintaining the effect of interference re-radiation between the conductive metal layers reflecting with respect to IR radiation, the dual highly selective structure of the formation of a thin-film coating of the product in the form of two successive series of layers "contact layer - catalytic layer - silver layer reflecting infrared radiation - barrier layer ”is separated by a sufficiently thick optically transparent dielectric layer, commonly called an intermediate layer, the thickness of which is generally several tens of nanometers, depending on the degree of spectral broadening to be achieved. Within the framework of the present invention, based on the conditions below, 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 it was 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 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, as a rule, acquiring an increased diffusion coefficient, which is characteristic of substoichiometric aluminum nitrides. mobility with thermal energy in the course of heating the substrate during heat treatment - first of all, oxygen atoms from oxide layers. This, in turn, prevents the flow of reaction radicals to the layer of silver Ag reflecting IR radiation that 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 aggregation of conductive layers of a thin-film optical coating by reaction processes on diffusing radicals, 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 coefficient of transparency of the product by increasing the total total thickness of the electroconductive metal layers absorbing electromagnetic radiation in the visible range of wavelengths, in the role of which in the layer structure of the heat-resistant highly selective energy-saving bronze-colored coating on the 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 terms of 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 layers of the coating. 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 thermostable energy-saving coating - the first contact, the first catalytic, the first reflecting IR radiation and the first barrier layers: as a material of the second contact layer applied over and in direct contact with the previous intermediate layer with respect to the surface of the glass substrate 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 nichrome oxide Ni-Cr-O is used as the material of the next layer, which is the second barrier layer.

колориметрии в светоотражении с поверхности стеклянной подложки со стороны, противоположной стороне, на которую нанесено тонкопленочное энергоэффективное оптическое покрытие, достигающим свыше 10 единиц по каждой из осей двухмерного колориметрического квазипространства. В результате, для минимизации указанного эффекта, и с целью контроля уровня смещения баланса светопропускания/поглощения слоевой структуры покрытия в результате термообработки в диапазоне, обеспечивающем возможность достижения желаемого насыщенного бронзового оттенка светоотражения со стороны, противоположной стороне, на которую нанесено тонкопленочное энергоэффективное оптическое покрытие, в широком диапазоне углов наблюдения, а также для юстировки величины смещения положения по цветовым квазикоординатам а*/b* стандарта CEILAB

колориметрии светоотражения изделия в ходе термообработки, после второй слоевой группы высокоселективной энергоэффективной тонкопленочной конструкции, состоящей из второго ИК-отражающего серебряного слоя и соприлегающих ему второго контактного, второго каталитического и второго барьерного слоев, непосредственно поверх второго барьерного слоя, содержащего субстехиометрический оксид нихрома Ni-Cr-O, наносится обеспечивающий избыточное поглощение в видимом диапазоне длин волн электромагнитного излучения слой, в качестве материала которого в рамках настоящего изобретения был выбран субстехиометрический нитрид вольфрама W-N, и который традиционно называется поглощающим слоем. Выбор вольфрама в качестве металлической компоненты материала поглощающего слоя связан с тем, что данный металл обладает оптимальными оптическими характеристиками с точки зрения баланса индекса рефракции и коэффициента экстинкции, достигающими значений 3,774 и 2,634 единиц на длине волны 0,77μм соответственно. За счет этого, при использовании вольфрама в качестве металлической компоненты материала поглощающего слоя достигается оптимальный уровень требуемого поглощения в видимой части спектра электромагнитного излучения уже на толщинах поглощающего слоя, которые будут достаточно малы, чтобы избежать существенного ступенчатообразного спада светопропускания изделия, в том числе в ходе его термообработки, за счет протекания паразитных процессов интерференционного характера при преодалении электромагнитным излучением всей совокупности слоев тонкопленочной структуры. Одновременно с этим также реализуется эффект компенсации спектрального уширения в диапазоне длин волн порядка 380-810 нм, за счет чего включение слоя данного материала в слоевую структуру покрытия не вносит прямого искажения в поведение спектральных кривых пропускания и отражения изделия, в ходе сопутствующей стабилизации положения по цветовым квазикоординатам а*/b* стандарта CEILAB

колориметрии светоотражения в светоотражении с поверхности стеклянной подложки со стороны, противоположной стороне, на которую нанесено тонкопленочное энергоэффективное оптическое покрытие изделия в ходе термообработки. При этом, осаждение слоя в виде субстехиометрического нитрида обеспечивает данному слою необходимые барьерные качества, связанные с характерным для субстехиометрических нитридов вольфрама сниженным коэффициентом диффузии сквозь осажденный слой реакционных компонент из вышележащих, внешних по отношению к данному слою соотносительно подложке слоев, как правило приобретающих повышенную диффузионную подвижность с тепловой энергией в ходе нагрева подложки при термической обработке - прежде всего, атомов кислорода, приходящего в ходе процесса термообработки с атмосферы.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 article, 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 Ag layers and adjacent catalytic layers, the layer structure of the coating collectively demonstrates resulting increase in transmittance relative to the visible range of wavelengths of electromagnetic radiation with a concomitant, often significant, shift in position along the color quasi-coordinates a * / b * of the CEILAB standard

colorimetry in 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, reaching more than 10 units along each axis of the two-dimensional colorimetric quasi-space. As a result, in order to minimize this 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 bronze 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 viewing angles, as well as for adjusting the value of the position shift according to the color quasi-coordinates a * / b * of the CEILAB standard

colorimetry of light reflection of the product during heat treatment, after the second layer group of a highly selective energy-efficient thin-film structure, consisting of a second IR-reflective silver layer and adjacent second contact, second catalytic and second barrier layers, directly on top of the second barrier layer containing substoichiometric nichrome oxide Ni-Cr -O, a layer providing excessive absorption in the visible wavelength range of electromagnetic radiation is applied, the material of which in the framework of the present invention has been chosen substoichiometric tungsten nitride WN, 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 from the point of view of the balance of the 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. Simultaneously with this, 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 by color quasi-coordinates a * / b * of the CEILAB standard

colorimetry of light reflection in 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 of the article 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. 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 reflectivity in the infrared region of the spectrum. In this case, the second covering layer should 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 deep into 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 properties 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 the thin-film layer of Si-Al-N is extremely small in comparison with the semitransparent layers of the subsequent deposited thin-film metal, during the passage of electromagnetic radiation of the visible range of wavelengths through the entire the 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. Similarly, in order to minimize the final additional decrease in the coefficients of translucency 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 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 requirements presented above, it also, as it was empirically determined, provides, with a layer thickness that is in the permissible range of values, the reasons for the establishment of 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 a 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 show the required level of crack propagation suppression (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 the 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 the 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, deposited on 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 wavelength range of electromagnetic radiation to the region of the order of 620-800 nm through appropriate adjustment of the individual thicknesses of the group of layers adjacent to the first and the second functional layers of silver Ag within the values described below - namely: the first and second contact, catalytic and barrier layers containing oxide doped with tin zinc Zn-Sn-O, oxide doped with aluminum zinc Zn-Al-O and substoichiometric oxide nichrome 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.

значением, лежащим в пределе от +0,6 до +9,5 относительных единиц, для обеспечения бронзового цвета отражения поверхности стеклянной подложки со стороны, противоположной стороне, на которую нанесено тонкопленочное энергоэффективное оптическое покрытие, за счет отсутствия вклада в результирующее положение по цветовым квазикоординатам зеленой компоненты, из-за которой итоговый цвет будет восприниматься смещенным в голубую часть видимого спектра по УФ-границе. Исходя из этих двух противоречивых требований, был определен диапазон допустимых значений толщины промежуточного слоя, содержащего субстехиометрический нитрид алюминия Al-N, составляющий от 35 нм до 57 нм.The choice of the thickness of the intermediate layer containing substoichiometric aluminum nitride Al-N, ranging from 35 nm to 57 nm, is determined by two main conditions: the thickness of this layer must, on the one hand, be no 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 provide the effect of interference attenuation during re-radiation between the layers of silver Ag, reflecting IR 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 33% with a concomitant increase in the product selectivity coefficient S to a value of at least 1.346 units. On the other hand, the thickness of the intermediate layer should be no more than half of the multiple of at least one of the radiation wavelengths of the visible spectrum range corresponding to the color perception of human vision, characterized along the a * axis of the green / red color differentiation of the quasi-coordinate grid of the international standard CEILAB

a value lying in the range from +0.6 to +9.5 relative units to ensure a bronze color 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, due to the absence of a contribution to the resulting position by color quasi-coordinates the green component, due to which the final color will be perceived to be shifted to the blue 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 35 nm to 57 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 21 nm to 32 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 transparency, characterized by the transmittance of visible radiation T _vis , which is at least 37 %. 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 21 nm to 32 nm.

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 0.8 to 1.7. As it was experimentally found, when the ratio of the thicknesses of these layers is less than 0.8 (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 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 outer "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 silicon nitride doped with aluminum Si-Al-N to the total thickness of the second covering layer containing substoichiometric aluminum nitride Al-N, and the outer layer containing oxide doped with zinc tin Zn -Sn-O exceeding 1.7 (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 simultaneously 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 with respect 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 ...

в направлении меньших значений, соответствующих зеленым оттенкам человеческого цветовосприятия, с сохранением возможности достижения положения по оси а* колориметрических квазикоординат, соответствующего значениям, не менее +0,6 относительных единиц, что согласуется с техническим результатом настоящего изобретения. Одновременно с этим, отношение толщины первого слоя, отражающего ИК излучение, содержащего серебро Ag, к толщине второго слоя, отражающего ИК излучение, содержащего серебро Ag, не должно превышать 0,41 с тем, чтобы интерференционный резонансный пик, приходящийся на видимую часть спектра электромагнитного излучения, при переизлучении между серебряными слоями высокоселективной платформы продукта с двумя отражающими ИК-излучение слоями наблюдался на длине волны не больше половины величины, кратной как минимум одной из длин волн излучения видимого диапазона спектра, соответствующих цветовому восприятию человеческого зрения, характеризуемому по оси b* цветовой дифференциации желтый/синий квазикоординатной сетки международного стандарта CEILAB

значением, лежащим в пределе от +7,7 до +14,6 относительных единиц, для обеспечения насыщенного бронзового цвета отражения поверхности стеклянной подложки со стороны, противоположной стороне, на которую нанесено тонкопленочное энергоэффективное оптическое покрытие во всем диапазоне углов наблюдения относительно нормали к поверхности подложки.The total thickness of two layers of infrared reflecting thin-film heat-resistant highly selective energy-saving coating of the article containing silver Ag is adjusted so that the surface ohmic resistance of the article does not exceed 2.27 Ohm / □, and only in this case is the cumulative balance between the emissivity of the article realized, with the emissivity ε not exceeding 3.2%, and the value of the transmittance of electromagnetic radiation in the visible range of wavelengths T _vis , which is not less than 37%, as a result of which the product possesses the qualities of high selectivity, expressed in achieving the selectivity coefficient S of not less than 1.346. In this case, the ratio of the thickness of the first IR reflecting layer containing silver Ag to the thickness of the second IR reflecting layer containing Ag silver should be in the range from 0.29 to 0.41. The lower of the indicated limits is due to the fact that, as it was experimentally shown, only at values of 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 0.29 antiphase resonant attenuation at wavelengths of the near ultraviolet region will not affect the shift of 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

in the direction of lower values corresponding to the green shades of human color perception, while maintaining the possibility of achieving the position along the a * axis of the colorimetric quasi-coordinates corresponding to values of at least +0.6 relative units, which is consistent with the technical result of the present invention. 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 0.41 so that the interference resonance peak falling on the visible part of the electromagnetic spectrum radiation, when re-radiation between the silver layers of a highly selective product platform with two reflective layers of IR 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 range of the spectrum corresponding to the color perception of human vision, characterized by the color b * axis differentiation yellow / blue quasi-coordinate grid of the international standard CEILAB

a value lying in the range from +7.7 to +14.6 relative units, to ensure a saturated bronze color of reflection of the glass substrate surface from the side opposite to the side on which the thin-film energy-efficient optical coating is applied in the entire range of viewing angles relative to the normal to the substrate surface ...

а* и b*, достигаемый юстировкой отношения толщин отражающих ИК-излучение тонкопленочных слоев покрытия, содержащих серебро Ag, и толщины промежуточного слоя, содержащего субстехиометрический нитрид алюминия Al-N в рамках указанных и объясненных выше пределов, что обеспечивает бронзовый цвет отражения поверхности стеклянной подложки со стороны, противоположной стороне, на которую нанесено тонкопленочное энергоэффективное оптическое покрытие. Кроме того, эмпирически было выявлено, что отношения толщины первого барьерного слоя, который содержит субстехиометрический оксид нихрома Ni-Cr-O, к совокупной толщине первого контактного слоя, содержащего оксид легированного оловом цинка Zn-Sn-O, и первого каталитического слоя, содержащего оксид легированного алюминием цинка Zn-Al-O, и толщины второго барьерного слоя, который содержит субстехиометрический оксид нихрома Ni-Cr-O, к совокупной толщине второго контактного слоя, содержащего оксид легированного оловом цинка Zn-Sn-O, и второго каталитического слоя, содержащего оксид легированного алюминием цинка Zn-Al-O, также не должны, с другой стороны, превышать значения 0,27, для того, чтобы также исключить влияние паразитного дополнительного остаточного переизлучения между этими двумя функциональными группами слоев высокоселективной платформы изделия с двумя отражающими ИК-излучение тонкопленочными слоями на эффект спектрального уширения от промежуточного слоя, содержащего субстехиометрический нитрид алюминия Al-N.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 13⋅10 ^-3 so that the parasitic additional residual re-radiation between these two functional groups of the layers of a highly selective product platform with two thin-film layers reflecting IR radiation does not have a shifting effect on the balance of the position by color coordinates quasi-coordinate grid of the international standard CEILAB

a * and b *, achieved 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 provides a bronze color of the reflection of the glass substrate surface from the side opposite to the side on which the thin-film energy-efficient optical coating is applied. In addition, it was 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 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, on the other hand, should also not, on the other hand, exceed the value 0.27, 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 1.3 to 12.5. 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 1.3, excessive resonance effects on the transmission spectrum of electromagnetic radiation in the near infrared wavelength range of the order of 810-1130 nm and the visible wavelength range of the order of 430-540 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 nanoscale layers of silver Ag by radiation falling on the coating, along with a simultaneous decrease in the light transmission of the entire cumulative thin-film layer structure of the described product in the visible wavelength range T _{v is} due to a 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 12.5, was selected based on the fact , that, as it was empirically determined, when the ratio exceeds this value, the thickness of the second barrier layer containing substoichiometric oxide of nichrome Ni-Cr-O becomes so great that this leads to the induction of parasitic stresses at the boundary of this layer and lying immediately below it with respect to glass substrate of the article of the second layer reflecting infrared radiation, which contains silver Ag, the allowable thickness of which, in turn, is selected in the range and proceeding from the conditions noted and explained above. Due to this, degradation of 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 0.56 to 24.25 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 24.25, 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 the indicated 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 qualities of ensuring uniform growth of the silver Ag layer, which is deposited on top of it relative to the glass substrate of the product, the permissible thickness of which, in turn, is selected in the range and based on the conditions noted and explained above, through the subsequent translation of the features of the structure subjected to recrystallization effects of the contact layer 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 the oxide doped with aluminum zinc Zn-Al-O, less than the value of the lower permissible limit of 0.56, the thickness of the catalytic layer will obviously prevail over the thickness of the underlying relative to the glass substrate products of the contact layer, and to a sufficient extent so that this difference in the thicknesses of these layers negatively affects the adhesion properties of the contact layer containing tin-doped zinc oxide Zn-Sn-O, due to the induction of parasitic into the layer, associated mainly with interstitial defects , stresses from the side of a thick layer of oxide doped with aluminum zinc and 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 0.56, 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 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 0.56 at the lower boundary and up to 24.25 along the upper border.

в ходе термического воздействия на тонкопленочную слоевую структуру покрытия изделия при термообработке будет недостаточен для подавления смещения баланса светопропускания/поглощения слоевой структуры покрытия в результате термообработки в диапазоне, обеспечивающем возможность достижения желаемого насыщенного бронзового оттенка светоотражения со стороны, противоположной стороне, на которую нанесено тонкопленочное энергоэффективное оптическое покрытие, в широком диапазоне углов наблюдения, а также для юстировки величины смещения положения по цветовым квазикоординатам а*/b* стандарта CEILAB

колориметрии светоотражения изделия в ходе термообработки менее 3 единиц по каждой из индивидуальных координат колориметрического квазипространства. Последнее приводит к потере возможности обеспечения необходимого насыщенного бронзового оттенка изделия в случае светоотражения с поверхности стеклянной подложки со стороны, противоположной стороне, на которую нанесено тонкопленочное энергоэффективное оптическое покрытие, достигаемого в широком диапазоне углов наблюдения и характеризуемого следующими параметрами оттенка отражения в цветовых квазикоординатах а*/b* международного стандарта CEILAB

а* от +0,6 до +9,5, и b* от +7,7 до +14,6, согласно заявленному в технической задаче настоящего изобретения. Исходя их вышеприведенных противоречивых требований, было установлено, что толщина поглощающего слоя, который содержит субстехиометрический нитрид вольфрама W-N, должна поддерживаться на уровне, союстированном с толщинами прочих слоев описываемого термоустойчивого энергоэффективного покрытия, выбранных согласно прочим изложенным требованиям к изделию, таким образом, что результирующее прямое пропускание электромагнитного излучения в диапазоне 385-790 ТГц термоустойчивого высокоселективного энергосберегающего покрытия бронзового цвета на стекле будет находиться в пределах строго от 0,36 до 0,53.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 bronze-colored coating on glass is from 0.36 to 0.53. In the event that 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 the product of electromagnetic radiation in the range 385-790 THz will be less than 0.36, 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 transmission of visible radiation T _vi declared in the technical problem of the present invention _s within no less than 37%. 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 product's direct transmission of electromagnetic radiation in the range 385 -790 THz will exceed 0.53. As a result, the effect of suppressing the growth of the transmittance 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, provided by the absorbing layer of substoichiometric tungsten nitride WN

in the course of thermal action on the thin-film 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 the range that makes it possible to achieve the desired saturated bronze hue of light reflection from the side opposite to the side on which the thin-film energy-efficient optical coverage, in a wide range of viewing angles, as well as for adjusting the value of the offset position according to the color quasi-coordinates a * / b * of the CEILAB standard

colorimetry of light reflection of the product during heat treatment less than 3 units for each of the individual coordinates of the colorimetric quasi-space. The latter leads to the loss of the possibility of providing the necessary saturated bronze 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, which is achieved in a wide range of viewing angles and is characterized by the following parameters of the reflection shade in color quasi-coordinates a * / b * international standard CEILAB

a * from +0.6 to +9.5, and b * from +7.7 to +14.6, 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 bronze-colored coating on the glass will be strictly within the range from 0.36 to 0.53.

The limit on 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 0.7, 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 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 the 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, 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, a selectivity S of at least 1.346.

At the same time, the thickness of the outer "SPT" -layer containing zinc-doped tin oxide Zn-Sn-O should be at least 7 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 the layer components into submicron and micron globular crystalline formations over the underlying one, containing substoichiometric aluminum nitride Al-N and being the second covering, as well as protective - to provide chemomechanical protection of the entire previously listed structure of the layers - the layer required appropriate thickness. 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 outer "PRT" -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 applied 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 an abrupt change in the substrate temperature, for example, during thermal quenching, which consists in rapid heating and subsequent abrupt cooling of the article, 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 7 nm.

In addition, the total 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 20 nm. This is due to the fact that these two layers external 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. 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 the 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 providing a sufficient loss of excess kinetic energy, and, as a consequence, the loss of initial mobility by radicals. This limit was found to be 20 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.

At the same time, in a particular case, it is proposed to connect 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 a 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 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 shock 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 a method of obtaining the described highly selective energy-saving coating of bronze color 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 the substoichiometric nitride of aluminum-doped silicon Si-Al-N is carried out by sputtering a bimetallic alloy doped with aluminum SiAl 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 bimetallic alloy of silicon doped with aluminum SiAl of the sputtered target should be from 2% to 60%. At a doping level of 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 bimetallic 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, 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 layers of the layer 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 bimetallic alloy doped with aluminum silicon SiAl with a doping level of 2 % up 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 bimetallic 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 injected 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 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 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 bimetallic alloy doped with tin zinc ZnSn of the sputtered target should be from 5% to 80%. When sputtered bimetallic targets are used 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 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 9.4⋅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 high values during the heat treatment of the product due to further aggregation effects of functional reflective IR radiation of layers of silver Ag, which underwent the initial translation of the recrystallized structure of the underlying layers in the course of 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 a metal sputtering target in the magnetron discharge plasma from a bimetallic alloy of tin-doped zinc ZnSn with an alloying degree of 5% 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 a metal sputtering target from a bimetallic alloy doped with aluminum zinc ZnAl 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 injected 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 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 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 bimetallic 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 the bimetallic alloy doped with tin zinc ZnSn, given above. ... When using sputtered bimetallic 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 promote the processes of recrystallization of a thin film during the formation of an excessively large amount 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 9.4⋅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 high values during the heat treatment of the product due to further aggregation effects of functional reflective IR radiation of layers of silver Ag, which underwent the initial translation of the recrystallized structure of the underlying layers in the course of direct formation. As a result, the deposition of the first catalytic layer containing the oxide of aluminum-doped zinc Zn-Al-O should be carried out by sputtering in the magnetron discharge plasma a metal sputtering target made of a bimetallic alloy of aluminum-doped zinc ZnAl with a doping level of 5% to 80%.

The subsequent layer, reflecting infrared radiation and containing silver Ag, should be deposited by sputtering a metal target consisting of solid Ag silver with an impurity metal purity of at least 87%. 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 take place, both of the Ag layer 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 IR reflecting layer 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 9.4-10 ^-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 87% 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 from a bimetallic 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 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 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 bimetallic alloy of the target, its concentration in the composition of the deposited layer will also be less than the empirically established lower 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 altered 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 9.4-10 ^-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 has undergone 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 serves as the first covering layer, should be carried out by sputtering in the plasma of a magnetron discharge of a dielectric target made of ceramic stoichiometric oxide of a bimetallic 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 necessary 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, minimization of the negative impact of the highly reactive oxygen component on the previously deposited components is ensured: an 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 aluminum-doped zinc oxide 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 of zinc doped with aluminum Zn-Al-O, by reactive 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 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 interstitial defects beforehand, as a covering layer of zinc oxide doped with aluminum Zn-Al-O, thick enough to protect them, manages to form on top of 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 totality of the product qualities declared in the technical result of the present invention. At the same time, the reasons why the degree of alloying 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 the target made of bimetallic alloy doped with aluminum zinc ZnAl, with which, as described above, the first catalytic layer containing oxide doped with aluminum zinc Zn-Al-O should be deposited: when using ceramic sputtering targets of stoichiometric oxide of bimetallic alloy doped with aluminum zinc ZAO 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 promote the processes of recrystallization of a thin film during the formation of excess about 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 the second all-metal functional silver Ag layer reflecting IR radiation, as a result of which an increase in the value of the turbidity of the glass substrate with applied on it with an energy-efficient coating to values exceeding the value of 9.4⋅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 in the course of direct formation. Thus, the deposition of the first covering layer containing the oxide doped with aluminum zinc 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 bimetallic 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 a 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 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 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 limitation 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 defined and justified above. As a result, both 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 article deposited on top of it, during the translation of the morphology of the intermediate layer subjected to initial local aggregation, will occur, 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 9.4⋅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 Al 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 carried out 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 chosen scheme for constructing a thin-film optical energy-saving coating of the product assumes, for the above reasons , the 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 oxide of nichrome 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 a metal sputtering target made of a bimetallic alloy of tin-doped zinc ZnSn with an alloying degree of 5% to 80%, the deposition of the second the catalytic layer containing aluminum-doped zinc oxide Zn-Al-O should be carried out by sputtering a metal sputtering target made of a bimetallic alloy doped with aluminum zinc ZnAl with a degree of alloying from 5% to 80% in the magnetron discharge plasma, deposition of a thin-film silver Ag layer, which is the second a layer reflecting IR radiation should be carried out by sputtering a sputtering cathode target made of silver Ag with an impurity purity of at least 87% in the magnetron discharge plasma, and the deposition of the second barrier layer containing substoichiometric nichrome oxide Ni-Cr-O should be carried out by sputtering in the plasma of a magnetron discharge of a metal sputtering target made of a bimetallic alloy of an alloy of nichrome NiCr with a partial nickel concentration of at least 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 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 tungsten mass W. This, in turn, makes it 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 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 limitation 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 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 defined 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 increasing 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 9.4⋅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 that provides chemomechanical protection of the entire previously listed layer structure, and contains a 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 not less than 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 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 limitation 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 defined and justified above. As a result, both direct recrystallization of a thin film of the layer of substoichiometric aluminum nitride Al-N containing an excessive amount of impurity components will occur, as well as 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, which contains zinc-doped tin oxide Zn-Sn-O, during the 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 of this, 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 9.4⋅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 negatively affect the properties of the overall chemomechanical stability of the entire thin-film heat-resistant high-selective energy-saving bronze-colored coating on the glass substrate as a whole. Thus, the deposition of the second covering layer containing substoichiometric aluminum nitride Al-N should be carried out by sputtering a sputtering cathode target made of A1 aluminum with an impurity purity of at least 84% in the magnetron discharge plasma.

The outer layer of the entire structure of the coating layers, which acts as a "PRT" -layer and contains oxide doped with zinc tin Zn-Sn-O, is deposited by sputtering a cathode target from a bimetallic alloy doped with tin zinc ZnSn with a doping degree 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 injected 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 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 discharge burning into the arc mode, in which the surface of the sputtered target is damaged, 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 bimetallic 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 bimetallic targets with degrees of doping outside the above limits, the difference between the concentrations of the main and alloying metal the component of the deposited layer will be large enough to facilitate the processes of recrystallization of the 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 have a negative effect on the level of the "PRT" layer-properties and, as a result, degradation of the mechanical stability of the thin-film layer. coating of the described product during heat treatment, as a set of processes that provoke the redistribution of internal stresses in the thicker layer structure subjected to heating. As a result, for the above reasons, the deposition of a layer external 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 bimetallic 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 bimetallic alloy doped with aluminum silicon SiAl and aluminum Al should be maintained in the range from 420 to 610 V. This limitation on the range of permissible operating values of the combustion voltage of a magnetron discharge when sputtering the indicated cathode targets is associated 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 for knocking 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, according to the results 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 relative adhesion of the deposited layers to the surface to be deposited, and the stability of the immediately forming thin-film layer from the point of view 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 bimetallic alloy of aluminum-doped silicon SiAl and from aluminum Al along the upper limit, which is 610 V, the dynamics of accumulation of a parasitic positive charge on the surface of cathode targets of these materials sputtered into states of surface poisoning, corresponding to the levels of flows of puffing 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 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 poisoned target surfaces. In this case, the disruption of the discharge burning into 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 bimetallic 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 545 V. This restriction on the range of permissible operating voltage values of the 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 will be insufficient to knock out zinc atoms from the target surface, as well as aluminum - for the case of bimetallic alloy targets zinc doped with aluminum 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 arrival of a flux of sputtered atoms on 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 deposited surface 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 bimetallic alloy doped with tin zinc ZnSn and from a bimetallic alloy doped with aluminum zinc ZnAl along the upper limit, which is 545 V, the dynamics of accumulation of a parasitic positive charge on the surface of the cathode targets indicated materials sprayed in states of surface poisoning, corresponding to the levels of flows of puffing of 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 area of which will be initiated on the poisoned target surfaces. In this case, the disruption of the discharge burning into 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 bimetallic alloy of nichrome NiCr and tungsten W, ranging from 550 to 670 V. This restriction on the range of permissible operating values of the combustion voltage of a magnetron discharge when sputtering 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 will be insufficient to knock out nickel Ni atoms from the target surface from the nichrome NiCr bimetallic alloy, and from the target surface from tungsten W atoms, respectively, 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 deposited atoms on the substrate, would allow them to provide 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 the magnetron discharge is exceeded during sputtering of cathode targets made of a bimetallic alloy of nichrome NiCr and tungsten W along the upper limit of 637 V, the dynamics of accumulation of a parasitic positive charge on the surface of the cathode targets of these materials, sputtered in states of poisoning surfaces 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 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 an arc discharge, whose shadow area will be initiated on the poisoned target surfaces. In this case, the disruption of the discharge burning into 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, when sputtering cathode targets made of silver Ag, the burning voltage of a magnetron discharge should not exceed 560 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 on the surface of the substrate and over the entire area. the 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 emissivity of the product specified by the surface ohmic resistance of the thin-film coating, not exceeding 2.27 Ohm / □, 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 growth of parasitic resistance at the boundaries of crystalline conglomerates of a thin-film silver layer.

In turn, when sputtering cathode targets made of ceramic stoichiometric oxide of a bimetallic alloy doped with aluminum zinc ZAO, the combustion voltage of the magnetron discharge is maintained at a level not lower than 600 V. from itself a ceramic oxide, when the target surface is sputtered by the incoming flow of ions from the combustion region of the magnetron discharge plasma, 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 bimetallic alloy doped with aluminum zinc ZAO and knocking out atoms of aluminum Al and zinc Zn from the surface of the target to form a flow 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 made of ceramic stoichiometric oxide of a bimetallic 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 bimetallic 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 bimetallic alloy doped with tin zinc ZnSn no more than 60 A, for cathode targets made of bimetallic alloy doped with aluminum zinc ZnAl not more than 90 A, for cathode targets made of bimetallic alloy nichrome NiCr, tungsten W and ceramic stoichiometric oxide of bimetallic alloy doped with aluminum zinc ZAO - no more than 90 A, and for cathode targets made of silver Ag is not 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 discharge current limit, which is individual for a specific target material, is introduced with the flow of sputtering ions from the magnetron discharge plasma into the unit of time reaches the value 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 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 applied thin-film structure of a thermally stable highly selective about an energy-saving bronze-colored coating on the glass.

In this case, the combustion of a magnetron plasma discharge during sputtering is maintained in the pressure range from 11⋅10 ^-4 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 11⋅10 ^-4 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 sputtering process 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 mode of over-sputtering of the near-streak region of the sputtered target, there will be an actual absence of the flow of the substance sputtered on the substrate coming to the substrate, as a result of which the deposition of individual layers of the thin-film structure of the thermally stable, highly selective energy-saving bronze-colored coating on the glass will be impossible. Based on these two opposing factors, the operating pressures during the sputtering of targets in the plasma of a magnetron discharge for all materials of cathode targets should be limited to the range from 11⋅10 ^-4 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.

In this case, when sputtering targets from a bimetallic alloy doped with tin zinc ZnSn, a bimetallic alloy doped with aluminum zinc ZnAl and a bimetallic alloy of nichrome NiCr, a reaction gas component is additionally admitted into the vacuum chamber, which is oxygen O ₂ , which contributes to the formation 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 1.86. Otherwise, when the total pressure of the working gases in the spray chambers is, as mentioned above, from 11⋅10 ^-4 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: bimetallic alloy doped with tin zinc ZnSn, bimetallic alloy doped with aluminum zinc ZnAl and bimetallic 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 bimetallic 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 on the surface of the glass substrate of the required layers of substoichiometric nitride doped with aluminum 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. In this case, the ratio of the value of the gas injection of nitrogen N ₂ to the value of the gas injection of argon Ar should be maintained in such a way 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 the alloy of silicon doped with aluminum 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 54. Otherwise, as was empirically determined, the dynamics of side ionization of atoms sputtered from the targets the corresponding substances in the course of their overcoming the combustion zone of the magnetron discharge will be too high for 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 stresses enclosed in the corresponding thin-film layers in the future, during the operation of the final product, and, most likely, during its exposure 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 bronze-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 4.12⋅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 framework of the described series, 8 samples of coatings were obtained. 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. Similarly, the corresponding materials and target composition (or impurity purity for monoelement targets) used in the process of sputtering in the magnetron discharge plasma are satisfied as described in the claims of the present invention.

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 burning 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 was used as the working gas for the sputtering of each of the used cathode targets. At the same time, for the deposition of oxide layers during sputtering of targets from a bimetallic alloy doped with tin zinc ZnSn, a bimetallic alloy doped with aluminum zinc ZnAl and a bimetallic alloy of 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 the sputtering of targets from a bimetallic alloy doped with aluminum silicon SiAl, from aluminum Al and from tungsten W, a reaction gas component, which was nitrogen N ₂ , was additionally admitted into the sputtering vacuum chambers. The control of the leakage flow value at the inlet of each of the components of the gas mixture was maintained using MKS P2A gas flow meters. In this case, in accordance with the claims, the ratio of the amount of gas injection of oxygen O ₂ to the value of the gas injection of argon Ar was maintained at a level not exceeding 1.86, 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 flow rate 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 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 and W, respectively, did not exceed 54. 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 with an analog-digital feedback loop connected to the gas flow meters of the nitrogen inlet N2-components of a mixture of working gases MKS P2A.

The obtained samples were subjected to temperature exposure 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 estimate of the standard deviation of the intensity value of the chromaticity index of a unit area of the sample surface from a sample of the full surface in monochrome display, an example of which is shown in FIG. 1, demonstrated that for all 8 samples obtained, the turbidity value does not exceed 0.0937%.

The transmission spectra for all 12 samples obtained within the framework of the described series of products in the UV / VIZ / IR range of electromagnetic radiation wavelengths 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, thereby effectively preventing the transmission of excess thermal solar radiation at wavelengths above 1200 nm. Along with this, the graphs of the transmission spectra reach saturation with an 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 at 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 40% to 42%, the solar factor g, ranging from 24% to 26%, selectivity S, ranging from 1.543 to 1.615 units, the coefficient of direct transmission of electromagnetic radiation in the range 385-790 THz, ranging from 0.44 to 0.48 fractions.

To determine the numerical normalization of the qualities of energy efficiency in terms 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 FT-IR spectrophotometer. 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 1.76 Ohm / □ before heat treatment in muffle furnaces, and 1.13 Ohm / □ 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 obtained samples the value of ε equal to 0.02 before heat treatment and 0.01 after heat treatment, which corresponds to the specified technical result.

(пример анализа представлен на фиг. 3) дает следующие значения по цветовым квазикоординатам: положение по оси цветовой дифференциации зеленый/красный квазикоординатной сетки а*, составляющее от +2,83 до +9,03 единиц; положение по оси цветовой дифференциации желтый/синий квазикоординатной сетки b*, составляющее от +12,83 до +13,44 единиц.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 CEILAB standard

(an example of the analysis is shown in Fig. 3) gives the following values for color quasi coordinates: position on the axis of color differentiation green / red quasi-coordinate grid a *, ranging from +2.83 to +9.03 units; position along the axis of color differentiation yellow / blue of the quasi-coordinate grid b *, ranging from +12.83 to +13.44 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 bronze-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 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 2.72⋅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, 12 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 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 bronze-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 was used as the working gas for the sputtering of each of the used cathode targets. At the same time, for the deposition of oxide layers during sputtering of targets from a bimetallic alloy doped with tin zinc ZnSn, a bimetallic alloy doped with aluminum zinc ZnAl and a bimetallic alloy of 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 the sputtering of targets from a bimetallic alloy doped with aluminum silicon SiAl, from aluminum Al and from tungsten W, a reaction gas component, which was nitrogen N ₂ , was additionally admitted into the sputtering vacuum chambers. The control of the leakage flow value at the inlet of each of the components of the gas mixture was maintained using MKS P2A gas flow meters. In this case, in accordance with the claims, the ratio of the amount of gas injection of oxygen O ₂ to the value of the gas injection of argon Ar was maintained at a level not exceeding 1.86, 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 flow rate 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 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 and W, respectively, did not exceed 54. 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 with an analog-digital feedback loop connected 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 layer of the coating containing zinc-doped tin oxide Zn-Sn -O, and further comparative characterization as described below.

The first part of the sample cuts, intended for characterization analyzes, was subjected to temperature exposure as a result of holding in Carbolite GLO 11-1G laboratory muffle furnaces at a temperature of 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 estimate of the standard deviation of the intensity value of the chromaticity index of a unit area of the sample surface from a sample of the full surface in monochrome display, an example of which is shown in FIG. 4, demonstrated that for all 12 samples obtained, the turbidity value does not exceed 0.0933%.

The transmission spectra for all 12 samples obtained within the framework of the described exemplary series of products in the UV / VIZ / IR range of electromagnetic radiation wavelengths of 250-1500 nm are shown in Fig. 5. The spectrum shows a sharp drop in the 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 reflective IR radiation layers, thereby effectively preventing the transmission of excess thermal solar radiation at wavelengths above 1200 nm. Along with this, the graphs of the transmission spectra reach saturation with an 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 at 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 39% to 46%, the solar factor g, ranging from 24% to 26%, selectivity S, ranging from 1.704 to 1.861 units, the coefficient of direct transmission of electromagnetic radiation in the range 385-790 THz, ranging from 0.40 to 0.45 fractions.

To determine the numerical normalization of the qualities of energy efficiency in terms 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 FT-IR spectrophotometer. According to the results of stratometric measurements, the surface ohmic resistance of the 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 / □ to 2.12 Ohm / □ before heat treatment in muffle furnaces, and from 1.18 Ohm / □ up to 1.43 Ohm / □ 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 obtained samples the value of ε equal to 0.02 before heat treatment and 0.01 after heat treatment, which corresponds to the specified technical result.

- пример анализа представлен на фиг. 6 - дает следующие значения по цветовым квазикоординатам: положение по оси цветовой дифференциации зеленый/красный квазикоординатной сетки а*, составляющее от +2,18 до +2,74 единиц; положение по оси цветовой дифференциации желтый/синий квазикоординатной сетки b*, составляющее от +12,89 до 14,40 единиц.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 CEILAB standard

- an example of analysis is shown 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 +2.18 to +2.74 units; position on the axis of color differentiation yellow / blue of the quasi-coordinate grid b *, ranging from +12.89 to 14.40 units.

При этом термическая закалка стеклянной подложки с нанесенным на ее поверхность термоустойчивым высокоселективным энергосберегающим покрытием бронзового цвета осуществлялась в печи для промышленной закалки листового стекла Glastone FC 500 при температуре нагрева 695°С на протяжении 320 сек. при равномерном профиле конвекции. Температурные профили по верхней и нижней поверхностям подложки относительно передаточных валов печи имели куполообразное распределение с выставкой «левый край-центр-правый край»: 685-692-690 по верхней поверхности; 660-674-670 нижней границе. Воздушный баланс составлял 65%, выставка сопел - 34 мм. В качестве дополнительной прозрачной подложки, обращенной к внешнему слою покрытия, содержащему оксид легированного цинком олова Zn-Sn-O, использовалось плоскополированное флоат-стекло M1 толщиной 4 мм. При этом фиксация соединенных подложек изделий осуществлялась жесткой алюминиевой рамкой с ее последующим заполнением по краю полимерным компаундом для герметизации стеклопакетных сборок вдоль всей торцевой поверхности совмещенных подложек.At the same time, joining the product with a heat-resistant, highly selective, energy-saving bronze-colored coating on a thermally hardened glass substrate with an additional transparent substrate facing the outer coating layer 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 achieved during the experiments and reflected above, obtained by characterizing products by UV / VIZ / IR and FT-IR spectrophotometry, contactless 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 CEILAB standard

In this case, thermal quenching of a glass substrate with a heat-resistant, highly selective, energy-saving bronze-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 695 ° C for 320 seconds. with a uniform convection profile. 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: 685-692-690 along the upper surface; 660-674-670 lower border. The air balance was 65%, the nozzle extension was 34 mm. Flat-polished float glass M1 4 mm thick 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 aligned substrates.

а* от +0,6 до +9,5, и b* от +7,7 до +14,6; и высокой селективности энергосберегающего покрытия на стеклянных подложках, характеризуемой величиной селективности S не менее 1,346 при соответствующих коэффициенте пропускания видимого излучения T_vis, составляющим не менее 37%, и величине излучательной способности изделия, задаваемой поверхностным омическим сопротивлением тонкопленочного покрытия, не превышающим 2,4 Ом/□.Thus, on the basis of the foregoing, the presented article with a heat-resistant highly selective energy-saving bronze-colored coating on glass, realized according to the above method, demonstrates the simultaneous manifestation of the qualities of thermal stability 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 temperature at a level not higher than 9.4⋅10 ^-2 % at permissible exposure temperatures not lower than 780 ° C for at least 15 minutes; as well as the bronze color of an energy-saving coating on glass substrates 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 in color quasi-coordinates a * / b * international standard CEILAB

a * from +0.6 to +9.5, and b * from +7.7 to +14.6; and a high selectivity of an energy-saving coating on glass substrates, characterized by a selectivity S of at least 1.346 with a corresponding transmittance of visible radiation T _{vis of} at least 37% and an emissivity of the product specified by the surface ohmic resistance of a thin-film coating not exceeding 2.4 Ohm / □.

Claims (4)

1. A heat-resistant, highly selective, energy-saving bronze-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 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, for neither m is followed by an intermediate layer containing substoichiometric aluminum nitride Al-N, the subsequent layer is the second contact layer and contains oxide doped with tin zinc Zn-Sn-O, followed by a layer containing oxide doped with aluminum zinc 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 listed structure of the coating layers and acts as a propagation of cracks in the "PRT" -layer, contains zinc-doped tin oxide Zn-Sn-O, while the thickness of the intermediate layer containing substoichiometric aluminum nitride Al-N is from 35 to 57 nm, and the thickness of the layer containing substoichiometric aluminum-doped silicon nitride Si-Al-N is from 21 to 32 nm, while 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 0.8 to 1.7, 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 bronze-colored coating on glass does not exceed 2.27 Ohm / □, and the ratio of the thickness of the first infrared reflecting layer containing silver Ag to the thickness and not the second layer reflecting infrared radiation containing silver Ag is from 0.29 to 0.41, 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 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 contact layer, containing oxide doped with tin zinc Zn-Sn-O, and the second catalytic layer containing oxide doped with aluminum zinc Zn-Al-O, are from 13⋅10 ^-3 to 0.27, and the ratio of the thickness of the second barrier layer, which contains a substoichiometric oxide nichrome Ni-Cr-O, to the thickness of the first barrier layer containing substoichiometric oxide of nichrome Ni-Cr-O, is from 1.3 to 12.5, while the ratio of the thickness of the first contact of the active 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 the second catalytic layer containing aluminum-doped zinc oxide Zn-Al-O is from 0.56 to 24.25, 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 bronze-colored coating on glass is from 0.36 to 0.53, 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 the oxide doped with aluminum zinc Zn-Al-O, is not less than 0.7, and the thickness of the outer "PRT" -layer containing oxide doped with zinc tin Zn-Sn-O, composition It is at least 7 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 at least 20 nm. 2. A heat-resistant, highly selective, energy-saving, bronze-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. 3. A heat-resistant, highly selective, energy-saving bronze-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 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 bronze-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 plasma of a magnetron discharge sputtering cathode targets in the following sequence: bimetallic alloy of aluminum-doped silicon SiAl with a degree of alloying ranging from 2 to 60%, bimetallic alloy of tin-doped zinc ZnSn with a degree of alloying from 5 to 80%, bimetallic alloy of aluminum-doped zinc ZnAl with a degree of alloying from 5 to 80%, silver Ag with an impurity purity of at least 87%, bimetallic alloy of nichrome NiCr with a partial concentration of nickel at least 10%, ceramic stoichiometric oxide of a bimetallic alloy doped with aluminum zinc ZAO with a degree alloying from 5 to 80%, aluminum Al with an impurity purity of at least 84%, bimetallic alloy doped with tin zinc ZnSn with a degree of alloying ranging from 5 to 80%, bimetallic alloy doped with aluminum zinc ZnAl with a degree of alloying ranging from 5 to 80% , silver Ag with an impurity purity of not less than 87%, bimetallic alloy of nichrome NiCr with a partial concentration of nickel 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 bimetallic alloy doped with tin zinc ZnSn with a degree of doping ranging from 5 to 80%, while the burning voltage of a magnetron discharge when sputtering cathode targets made of a bimetallic alloy of aluminum-doped silicon SiAl and aluminum Al is maintained in the range from 420 to 610 V, when sputtering cathode targets made of a bimetallic alloy doped with tin zinc ZnSn and from a bimetallic alloy alloyed with aluminum zinc ZnAl - in the range from 4 20 to 545 V, when sputtering cathode targets made of a bimetallic alloy of nichrome NiCr and tungsten W - in the range from 550 to 670 V, when sputtering cathode targets made of silver Ag, the burning voltage of a magnetron discharge does not exceed 560 V, and when sputtering cathode targets made of ceramic stoichiometric oxide of bimetallic alloy doped with aluminum zinc ZnAl, 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 bimetallic alloy doped with aluminum zinc ZnAl not more than 90 A, for cathode targets made of bimetallic alloy nichrome NiCr, tungsten W and ceramic stoichiometric oxide of bimetallic alloy doped with aluminum zinc ZAO - no more than 90 A, for cathode targets made of silver Ag no more than 15 A; In this case, the combustion of a magnetron plasma discharge during sputtering is maintained in the pressure range from 11⋅10 ^-4 to 4⋅10 ^-2 mbar for all materials of cathode targets, and argon Ar acts as a working gas, while sputtering targets made of a bimetallic alloy doped with tin zinc ZnSn, bimetallic alloy doped with aluminum zinc ZnAl and bimetallic 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 amount of gas supply of argon Ar does not exceed 1.86, and when sputtering targets from a bimetallic 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 gas inlet of nitrogen N ₂ to the value of the gas inlet of argon Ar is maintained so th 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 54.

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